Comprehensive Organic Synthesis [Complete 9 volume set]

Front Matter......Page 988
Preface......Page 990
Contributors to Volume 2......Page 992
Table of Contents......Page 995
1.1.1 Introduction......Page 997
1.1.2.1 General Considerations......Page 999
1.1.2.2 Reactions of Type I Crotyl Metal Reagents with Achiral Aldehydes, Ketones and Imines......Page 1005
1.1.2.3 Reactions of Type III Crotyl Organometallics with Achiral Aldehydes and Ketones......Page 1015
1.1.3.1 Reactions with Chiral Aldehydes......Page 1020
59299_v02_01_01b.pdf......Page 1026
Cumulative Subject Index......Page 0
1.1.3.2 Reactions with Chiral C=N Electrophiles......Page 1028
1.1.4.1 Chiral Allyl Organometallics with Conventional Auxiliaries......Page 1029
1.1.4.2 Chiral Allyl Organometallics with Stereocenters at C-1 or C-4......Page 1034
1.1.5 Double Asymmetric Synthesis: Reactions of Chiral C=X Electrophiles and Chiral Allyl Organometallics......Page 1036
1.1.6 Summary......Page 1042
1.1.7 Addendum......Page 1043
1.1.8 References......Page 1045
1.2.1 Synthetic Utility......Page 1050
1.2.2 Boron-Substituted Allylic Anions......Page 1051
1.2.3 Silicon-Substituted Allylic Anions......Page 1052
1.2.4 Nitrogen-Substituted Allylic Anions......Page 1055
1.2.5 Phosphine-Substituted Allylic Anions......Page 1059
1.2.6 Oxygen-Substituted Allylic Anions......Page 1061
1.2.7 Sulfur-Substituted Allylic Anions......Page 1066
1.2.8 Selenium-Substituted Allylic Anions......Page 1071
1.2.9 Halogen-Substituted Allylic Anions......Page 1072
1.2.11 References......Page 1073
1.3.3 Structure and Physical Properties......Page 1075
1.3.4.1 Non-Heteroatom-Substituted Propargyl or Allenyl Organometallics......Page 1076
1.3.4.2 Heteroatom-Substituted Propargyl and Allenyl Organometallics......Page 1082
1.3.5 Diastereoselective Reactions......Page 1085
1.3.6 Enantioselective Reactions......Page 1090
1.3.7 References......Page 1091
1.4.1 Introduction......Page 1093
1.4.2.1 Alkali Metal Enolates by Deprotonation of Carbonyl Compounds......Page 1094
1.4.2.2 Alkali Metal Enolates by Addition to alpha,beta-Unsaturated Carbonyl Compounds......Page 1100
1.4.2.3 Alkali Metal Enolates from Ketenes......Page 1101
1.4.2.4 Alkali Metal Enolates from Enol Acetates and Silyl Enol Ethers......Page 1102
1.4.2.5 Alkali Metal Enolates by Miscellaneous Methods......Page 1103
1.4.3 Magnesium Enolates......Page 1104
1.4.4 Boron Enolates......Page 1105
1.4.5 Aluminum Enolates......Page 1108
1.4.6 Tin Enolates......Page 1110
1.4.7 Titanium Enolates......Page 1111
1.4.9 Copper Enolates and Enolates from Cuprates......Page 1113
1.4.10 Zinc Enolates......Page 1116
1.4.11 Other Transition Metal Enolates......Page 1119
1.4.12 References......Page 1122
1.5.1 Introduction......Page 1126
1.5.3 Reversibility of the Aldol Reaction......Page 1127
1.5.5 Self-Reactions of Aldehydes......Page 1129
1.5.6 Mixed Reactions of Aldehydes......Page 1132
1.5.7 Self-Reactions of Ketones......Page 1133
1.5.9 Reactions of Ketones with Aldehydes......Page 1135
1.5.9.1 Acyclic Ketones......Page 1136
1.5.9.2 Cyclic Ketones......Page 1140
1.5.9.3 Alkylaryl and Related Ketones......Page 1143
1.5.9.4 Vinylogous Enolates......Page 1145
1.5.9.5 Stereochemistry......Page 1146
1.5.10.1 Dialdehydes......Page 1149
1.5.10.2 Keto Aldehydes......Page 1151
59299_v02_01_05b.pdf......Page 1152
1.5.10.3 Diketones......Page 1154
1.5.10.4 Stereochemistry of Aldol Cyclizations......Page 1159
1.5.10.5 Transannular Cyclizations......Page 1162
1.5.10.6 Polyketides......Page 1163
1.5.11 References......Page 1169
1.6.1 Introduction......Page 1173
1.6.2.1 Stoichiometric Deprotonation of Carbonyl Compounds......Page 1174
1.6.2.2 Regioselective Deprotonation of Ketones......Page 1175
1.6.2.4 Enolates from Conjugate Additions to alpha,beta-Unsaturated Carbonyl Compounds......Page 1176
1.6.2.5 Enolates from Reduction of alpha-Heteroatom-Substituted Carbonyl Compounds......Page 1178
1.6.2.6 Enolates of alpha,beta-Unsaturated Carbonyl Compounds......Page 1179
1.6.2.7 Dianions of Diketones and Keto Esters......Page 1181
1.6.3.1 General Overview......Page 1182
1.6.3.2 Ketone Enolates......Page 1184
1.6.3.3 Ester and Lactone Enolates......Page 1192
1.6.3.4 Carboxylic Acid Dianions (Ivanov Reaction)......Page 1202
1.6.3.5 Amide and Lactam Enolates......Page 1203
1.6.3.6 Thioester and Thioamide Enolates......Page 1206
1.6.4.1 Chiral Substrates......Page 1209
1.6.4.2 Chiral Enolates......Page 1215
1.6.4.4 Chiral Auxiliaries......Page 1224
1.6.5 Equilibration; Thermodynamic Control......Page 1226
1.6.6 References......Page 1227
1.7.1 Introduction......Page 1231
1.7.2.1 Preparation of Alkenyloxydialkylboranes......Page 1232
1.7.2.2 Diastereoselective Aldol Reactions (2,3-Stereochemistry)......Page 1236
1.7.2.3 Aldol Reactions Using Enantiomerically Homogeneous Alkenyloxydialkylboranes (3,4-Stereochemistry)......Page 1240
1.7.2.4 Aldol Reactions Mediated by Alkenyloxydialkoxyboranes......Page 1258
1.7.3.1 Preparation of Alkenyloxyalanes and Subsequent Aldol Reactions......Page 1260
1.7.3.2 Aldol Reactions Using Enantiomerically Homogeneous Alkenyloxydialkylalanes......Page 1263
1.7.4 References......Page 1265
1.8.1 Introduction......Page 1268
1.8.2.1 Isolation and Stability of Zinc Enolates......Page 1269
1.8.2.2 Structure of Zinc Enolates......Page 1271
1.8.3.1 Scope and Procedures......Page 1272
1.8.3.2 Chemoselectivity......Page 1274
1.8.3.3 Regioselectivity......Page 1276
1.8.3.4 Stereoselectivity......Page 1280
1.8.4 Reaction with Imines......Page 1285
1.8.5.1 Reaction with Esters and Acid Chlorides......Page 1287
1.8.5.2 Reaction with Nitriles, the Blaise Reaction......Page 1288
1.8.6 References......Page 1289
1.9.1 Introduction......Page 1291
1.9.2.1 Zirconium......Page 1292
1.9.2.2 Titanium......Page 1295
1.9.2.3 Rhodium......Page 1300
1.9.2.4 Cerium......Page 1301
1.9.3.1 Tungsten, Molybdenum and Rhenium......Page 1302
1.9.4.1 Cobalt......Page 1304
1.9.4.2 Iron......Page 1305
1.9.5 Other Asymmetric Aldol Reactions Involving Transition Metals......Page 1307
1.9.7 References......Page 1308
1.10.1 Introduction......Page 1310
1.10.2 General Considerations on the Nitroaldol Reaction and Its Utility in Organic Synthesis......Page 1311
1.10.3 Classical Nitroaldol Procedures and Their Limitations......Page 1314
1.10.3.1 Nitroaldol Reactions with Dialdehydes......Page 1315
1.10.3.2 Nitroaldol Reactions with Ketones......Page 1318
1.10.3.4 Regio- and Stereo-Selectivity in the Nitroaldol Reaction with alpha, beta-Unsaturated Aldehydes and Ketones......Page 1319
1.10.3.5 Significant Functionalized Nitroalkanes Used in Nitroaldol Reactions......Page 1320
1.10.4 Nitroaldol Reactions with Silyl Nitronates and with alpha, alpha Doubly Deprotonated Nitroalkanes......Page 1324
1.10.5 Addendum......Page 1327
1.10.6 References......Page 1328
1.11.1 Introduction......Page 1330
1.11.2.1 Reaction Conditions......Page 1332
1.11.2.2 Spectroscopy and Physical Properties......Page 1334
1.11.2.3 Mechanism......Page 1336
1.11.2.4 The Retro-Knoevenagel Reaction......Page 1338
1.11.2.5 Stereochemistry......Page 1339
1.11.2.6 Competitive Reactions......Page 1341
1.11.3.1 Variation of the Active Methylene Compound......Page 1343
1.11.3.2 Variation of the Carbonyl Compound......Page 1353
1.11.4 Sequential Reactions......Page 1358
1.11.5 Synthetic Applications......Page 1364
1.11.5.1 Carbocycles and Heterocycles......Page 1365
1.11.5.2 Natural Products and Biologically Active Compounds......Page 1370
1.11.5.3 Transformation of Sugars......Page 1374
1.11.5.4 Dyes and Polymers......Page 1376
1.11.7 References......Page 1377
1.12.1 Introduction......Page 1384
1.12.2 Mechanistic Considerations......Page 1385
1.12.3.1 Preparation of Cinnamic Acids and Related Aromatic Derivatives......Page 1388
1.12.3.2 Aliphatic Aldehydes and Ketones......Page 1389
1.12.3.3 Reparation of Coumarins......Page 1390
1.12.4.1 General and Mechanistic Considerations......Page 1391
1.12.4.2 Geometric Isomers of Oxazolone Products......Page 1392
1.12.4.3 Imines as Substrates......Page 1393
1.12.4.4 Rhodanine and Hydantoin Derivatives......Page 1395
1.12.5 References......Page 1396
1.13.1 Introduction......Page 1398
1.13.2 General and Mechanistic Considerations......Page 1400
1.13.3.1 Sulfur-Containing Groups......Page 1404
1.13.3.2 Nitriles......Page 1408
1.13.3.3 Lactones......Page 1409
1.13.3.4 Vinylogous Esters......Page 1410
1.13.3.6 Imines......Page 1411
1.13.3.7 Ketones......Page 1413
1.13.3.8 Carboxylic Acids......Page 1414
1.13.3.9 Silicon......Page 1415
1.13.4 Miscellaneous Modifications......Page 1416
1.13.5 Preparation of Aziridines......Page 1417
1.13.6.1 Phase-Transfer Conditions......Page 1418
1.13.6.2 Solid-Liquid Systems......Page 1423
1.13.7.1 Asymmetric Catalysis......Page 1424
1.13.7.2 Condensations Employing Asymmetric N-(alpha-Haloacetyl)Oxazolidinones......Page 1425
1.13.8 References......Page 1427
1.14.1 Introduction......Page 1429
1.14.3.1 Cyclopropane Ring Formation......Page 1431
1.14.3.2 Cyclopropane Ring Cleavage......Page 1432
1.14.5.1 Titanium Homoenolates......Page 1433
1.14.5.3 Other Metal Homoenolates......Page 1435
1.14.6.2 Zinc Homoenolates......Page 1436
1.14.7.1 Zinc Homoenolates......Page 1437
1.14.7.3 Silver Homoenolates......Page 1438
1.14.9 Synthetic Applications......Page 1439
1.14.9.3 Conjugate Addition......Page 1440
1.14.10 References......Page 1441
1.15.1 Introduction......Page 1443
1.15.3.1 Substrate Specificity......Page 1444
1.15.3.3 Enzyme Characteristics......Page 1449
1.15.3.4 Examples of FDP Aldolase in Organic Synthesis......Page 1450
1.15.4 N-Acetylneuraminic Acid Aldolase (E.C. 4.1.3.3)......Page 1451
1.15.5 Transketolase......Page 1452
1.15.6 KDO Synthetase......Page 1453
1.15.8 Conclusion and Future Perspectives......Page 1454
1.15.9 References......Page 1459
1.16.1 Introduction......Page 1462
1.16.2.1 Reactions of Imine Anions Derived from Aldimines......Page 1464
1.16.2.2 Reactions of Imine Anions Derived from 2-Azadienes......Page 1466
1.16.2.3 Reactions of Endocyclic Imine Anions Derived from Unsaturated Heterocycles......Page 1468
1.16.3.1 Phosphorus- and Silicon-Stabilized Imine Anions......Page 1469
1.16.4.2 Stabilized Oxime Anions......Page 1473
1.16.5.1 Acyclic Imidates......Page 1475
1.16.5.2 Metallated 2-Methyloxazolines......Page 1476
1.16.5.3 Metallated 2-Methyldihydro-1,3-Oxazines......Page 1479
1.16.5.5 Metallated 2-Methylimidazolines......Page 1481
1.16.6.1 2-Methyl Azaheteroaromatic Compounds......Page 1482
1.16.7.1 Asymmetric Synthesis of Amino Acids......Page 1485
1.16.8 References......Page 1488
1.17.1 Introduction......Page 1490
1.17.2 Preparation of Hydrazones from Aldehydes and Ketones......Page 1491
1.17.3 Formation of Azaallyl Metal Reagents from Hydrazones......Page 1493
1.17.4 Structures of Azaallyl Metal Reagents Derived from Hydrazones......Page 1494
1.17.5 Regiochemical and Stereochemical Control in Hydrazone Deprotonation......Page 1496
1.17.6 1,2-Additions to Aldehydes and Ketones......Page 1498
1.17.7 1,2-Additions to Carboxylic Acid Derivatives......Page 1503
1.17.8 1,4-Conjugate Additions to alpha,beta-Unsaturated Carbonyl Derivatives......Page 1504
1.17.9 Heterocycle Syntheses via 1,2- and 1,4-Additions of Hydrazone Anions to Carbonyl Compounds and alpha,beta-Unsaturated Carbonyl Compounds......Page 1507
1.17.11 Cleavage of Hydrazones to Regenerate Carbonyl Groups......Page 1510
1.17.12 References......Page 1512
2.1.1 Introduction......Page 1514
2.1.2.1 Formaldehyde......Page 1515
2.1.2.2 Electron-Deficient Aldehydes......Page 1521
2.1.2.3 Aliphatic and Aromatic Aldehydes......Page 1524
2.1.2.4 Ketones......Page 1525
2.1.3.1 Type I Reactions......Page 1527
2.1.3.2 Type II Reactions......Page 1534
2.1.3.4 Type III Reactions and Other Reactions of Acetals......Page 1540
2.1.4 Thiocarbonyl Compounds......Page 1542
2.1.5 Addendum......Page 1543
2.1.6 References......Page 1545
2.2.1 Introduction......Page 1549
2.2.2 Mechanism......Page 1550
2.2.3.1 Allylsilanes......Page 1553
2.2.3.2 Allylstannanes......Page 1558
2.2.3.3 Allenyl-, Propargyl-, Vinyl- and Ethynyl-Silanes and -Stannanes......Page 1561
2.2.4.1 Allylsilanes......Page 1562
2.2.4.2 Allylstannanes......Page 1564
2.2.4.3 Allenyl-, Propargyl-, Vinyl- and Ethynyl-Silanes......Page 1565
2.2.5.1 Allylsilanes and Allylstannanes......Page 1566
2.2.5.2 Vinylsilanes and Ethynylstannanes......Page 1567
2.2.6.1 Allylsilanes......Page 1568
2.2.6.3 Allenyl- and Propargyl-Silanes and -Stannanes......Page 1573
2.2.6.4 Vinyl-Silanes and -Stannanes......Page 1574
2.2.7 References......Page 1576
2.3.1 Introduction......Page 1580
2.3.2.1 Formation of Alkyl Enol Ethers and Enol Esters......Page 1581
2.3.2.2 Formation of Enol Silyl Ethers and Silyl Ketene Acetals......Page 1584
2.3.2.3 Formation of Enol Stannyl Ethers......Page 1592
2.3.2.4 Other Enol Ethers......Page 1595
2.3.3.1 Uncatalyzed Aldol and Related Condensations......Page 1596
2.3.3.2 Catalyzed Addition to C-X pi-Bonds and Equivalents......Page 1597
2.3.5 References......Page 1610
2.4.1 Introduction......Page 1614
2.4.2.1 Lewis Acid Mediated Additions to Aldehydes......Page 1615
2.4.2.2 Fluoride Ion Mediated Additions to Aldehydes......Page 1618
2.4.2.4 Lewis Acid Mediated Additions to Imines......Page 1620
2.4.3.1 Diastereoselective Aldol Additions of Chiral Silyl Ketene Acetals and Chiral Silyl Enol Ethers......Page 1621
2.4.3.2 Diastereoselective Additions of Chiral Silyl Ketene Acetals to Imines......Page 1623
2.4.4 Chiral Electrophiles......Page 1624
2.4.4.1 Diastereoselective Additions to Chiral Carbonyl Compounds......Page 1625
2.4.4.2 Diastereoselective Addition to Chiral Imines, Nitrones and 4-Acetoxyazetidin-2-Ones......Page 1632
2.4.4.3 Diastereoselective Additions to Chiral Iminium, Oxonium and Thionium Ions......Page 1634
2.4.4.4 Diastereoselective Additions to Chiral Acetals......Page 1635
2.4.4.5 Intramolecular Diasteroselective Aldol-Type Additions......Page 1636
2.4.5.1 Diastereoselective Additions of Chiral Silyl Ketene Acetals to Chiral Aldehydes......Page 1637
2.4.6 Chiral Lewis Acids......Page 1639
2.4.7 Addendum......Page 1640
2.4.8 References......Page 1642
2.5 Reactions of Activated Dienes with Aldehydes......Page 1646
2.5.1.2 Aldehydes as Dienophiles......Page 1647
2.5.1.3 Lewis Acid Catalysis......Page 1648
2.5.2.1 Thermal and High-Pressure Reactions......Page 1649
2.5.2.2 Lewis Acid Catalyzed Reactions......Page 1650
2.5.2.3 Comparison of Lewis Acid Catalysis: Analysis of Reaction Conditions......Page 1658
2.5.3.1 Cram-Felkin and Anti Cram-Felkin Stereochemical Control......Page 1662
2.5.3.2 The Effect of Lewis Acids on Diastereofacial Selectivity......Page 1663
2.5.4 Methods to Control Absolute Stereochemistry......Page 1665
2.5.4.2 Chiral Catalysts......Page 1666
59299_v02_02_05b.pdf......Page 1671
2.5.5.1 Simple Monosaccharides......Page 1674
2.5.5.2 3-Deoxy-D-Manno-2-Octulopyranosate (KDO)......Page 1677
2.5.5.5 Hikosamine......Page 1679
2.5.5.7 Spectinomycin Analogs......Page 1681
2.5.5.8 Tunicaminyluracil......Page 1682
2.5.5.9 Vineomycinone B_2......Page 1683
2.5.5.11 Lantin......Page 1684
2.5.5.13 6-Deoxyerythronolide B......Page 1685
2.5.5.15 Monensin Lactone......Page 1686
2.5.5.16 Tirandamycin......Page 1687
2.5.5.17 Rifamycin S......Page 1688
2.5.5.18 Zincophorin......Page 1689
2.5.6 References......Page 1690
3.1.1 Introduction......Page 1692
3.1.2.1 Mechanistic Aspects......Page 1693
3.1.3.1 Intermolecular Acylations......Page 1694
3.1.3.2 The Formation of Cyclic Ketones......Page 1695
3.1.3.3 The Use of Protic Acid......Page 1696
3.1.4.2 Alkenylsilanes......Page 1697
3.1.4.3 Allylsilanes......Page 1701
3.1.4.4 Acylations of Other Unsaturated Silanes......Page 1704
3.1.5.1 Simple Dienes......Page 1705
3.1.5.2 Diene Complexes......Page 1706
3.1.6.1 Simple Alkynes......Page 1708
3.1.6.2 Alkynylsilanes......Page 1710
3.1.7.1 Lewis Acid Catalyzed Acylations of Stannanes......Page 1711
3.1.8 Acylations of Alkanes......Page 1712
3.1.9 Aliphatic Formylation......Page 1713
3.1.10 References......Page 1714
3.2.1 Introduction......Page 1717
3.2.2 Mechanisms......Page 1718
3.2.3.1 Catalysts......Page 1719
3.2.3.3 The Sequence of Addition of the Reagents......Page 1722
3.2.4.1 Reactions Carried out in the Absence of Catalysts......Page 1723
3.2.4.2 Reactions Using Lewis Acid Catalysts......Page 1724
3.2.5 Fries Reactions......Page 1729
3.2.6 Reactions Using Nitriles - The Houben-Hoesch Synthesis......Page 1731
3.2.7 Vilsmeier and Related Ketone Syntheses......Page 1732
3.2.9 Gattermann and Related Formylation Reactions......Page 1733
3.2.10 References......Page 1734
3.3.1 Introduction......Page 1737
3.3.2 Electron Density Considerations......Page 1738
3.3.3 The Size of the Ring......Page 1739
3.3.3.1 Reactions Leading to the Formation of Five-Membered Rings......Page 1740
3.3.3.2 Reactions Leading to the Formation of Six-Membered Rings......Page 1742
3.3.3.3 Reactions Leading to the Formation of Seven-Membered Rings......Page 1747
3.3.5 References......Page 1750
3.4.2 The Normal Reaction......Page 1753
3.4.3 Scope and Limitations......Page 1754
3.4.4.1 Regioselectivity......Page 1755
3.4.4.2 Industrial Applications......Page 1756
3.4.5 The 'Abnormal' Reimer-Tiemann Reaction......Page 1757
3.4.6 The Mechanism of the Reaction......Page 1758
3.4.8 References......Page 1759
3.5.1 Introduction......Page 1760
3.5.3.1 Carbocyclic Compounds......Page 1762
3.5.3.2 Heterocyclic Compounds......Page 1763
3.5.4.1 Alkene Derivatives without Electron-Releasing Substituents......Page 1764
3.5.4.2 Alkene Derivatives with Electron-Releasing Substituents and Their Equivalents......Page 1766
3.5.5.1 Aldehydes and Ketones......Page 1768
3.5.5.3 Amides, Lactams and Lactones......Page 1769
3.5.5.5 Benzylic Methyl and Methylene Groups......Page 1772
3.5.6.1 Oxygen Nucleophiles......Page 1773
3.5.7.1 Hydrazones and Semicarbazones......Page 1774
3.5.8 References......Page 1775
3.6 Acylation of Esters, Ketones and Nitriles......Page 1778
3.6.1 Introduction......Page 1779
3.6.2 Mechanism......Page 1780
3.6.3.2 Mixed Esters and Unsymmetrical Diesters......Page 1782
3.6.3.3 The Dieckmann Reaction......Page 1789
3.6.3.4 Application to Synthesis......Page 1800
3.6.4.1 Introduction......Page 1812
3.6.4.2 Generation and Use of Enolates and Enol Ethers......Page 1813
3.6.4.3 Ketones as Enols: Acid Catalysis of Acylation......Page 1815
59299_v02_03_06b.pdf......Page 1816
3.6.4.4 Regiochemistry of Acylation......Page 1818
3.6.4.5 Synthetic Applications of Intermolecular Acylation of Ketones......Page 1820
3.6.4.6 Intramolecular Acylation of Ketones......Page 1826
3.6.4.7 Intramolecular Acyl Transfer......Page 1828
3.6.5.1 Chiral beta-Dicarbonyl Synthons......Page 1829
3.6.6.1 Mechanism......Page 1831
3.6.6.3 Scope of the Reaction......Page 1832
3.6.6.5 Application to Synthesis......Page 1834
3.6.7 Tandem Reactions......Page 1835
3.6.8.2 Cleavage of beta-Diketones......Page 1838
3.6.9 Conclusions......Page 1840
3.6.10 References......Page 1842
3.7.1 Introduction......Page 1847
3.7.2.1 alpha-Thioiminium Salt Formation......Page 1849
3.7.2.2 Sulfide Contraction and Carbon-Carbon Bond Formation......Page 1851
3.7.3.1 Knoevenagel-Based Modification......Page 1855
3.7.3.2 Thio-Wittig Modification......Page 1856
3.7.3.3 Preparation of beta-Dicarbonyl Compounds......Page 1857
3.7.4.1 Dendrobatid and Other Neurotoxic Alkaloids......Page 1858
3.7.4.2 Pyrrolidine Alkaloids......Page 1863
3.7.4.3 Quinolizidine, Pyrrolizidine and Related Alkaloids......Page 1864
3.7.4.4 Phosphodiesterase Inhibitor Analogs......Page 1867
3.7.4.5 Antibiotics......Page 1869
3.7.4.6 Nucleoside Analogs......Page 1871
3.7.4.7 Macrocycles......Page 1872
3.7.5 References......Page 1874
4.1.1.1 Introduction......Page 1875
4.1.1.2 Earlier Reviews and Scope of this Chapter......Page 1876
4.1.1.3 Mechanism......Page 1877
4.1.1.4 Scope and Limitations......Page 1878
4.1.1.5 New Modifications......Page 1879
4.1.2.2 Acyclic N,N-Dialkyliminium Salts......Page 1880
4.1.2.3 Cyclic Iminium Salts......Page 1894
4.1.2.4 N-Silyl- and N,N-Disilyl-Iminium Salts......Page 1895
4.1.3.1 Introduction......Page 1897
4.1.3.2 Acyclic N-Aryl- and N-Alkyl-Imines......Page 1898
59299_v02_04_01b.pdf......Page 1908
4.1.3.3 N-Heterosubstituted Imines......Page 1916
4.1.3.4 In Situ Methods......Page 1923
4.1.3.5 Cyclic Imines......Page 1924
4.1.5 References......Page 1930
4.2.1 Introduction......Page 1934
4.2.2 Mechanisms......Page 1935
4.2.3.1 Aminoalkylation Reactions of Phenols......Page 1937
4.2.3.3 Aminoalkylation Reactions of Other Carbocyclic Compounds......Page 1942
4.2.3.4 Reactions with Electron-Rich Heterocyclic Systems......Page 1943
4.2.4.2 Reactions Leading to Cyclic Products and Their Reactions......Page 1949
4.2.5 Reactions Using Imines......Page 1951
4.2.6 Amidoalkylation Reactions......Page 1952
4.2.7 References......Page 1953
4.3.1.1 Reactivity and Structure......Page 1955
4.3.1.2 Regio- and Stereo-Chemistry......Page 1958
4.3.2.1 Using Allyl Organometallic Reagents......Page 1960
4.3.2.2 Using Crotyl Organometallic Reagents......Page 1968
4.3.2.3 Using Propargyl/Allenic Organometallics......Page 1972
4.3.3.2 Oximes and Oxime Ethers......Page 1974
4.3.3.3 Sulfenimines......Page 1978
4.3.3.5 Sulfonylimines......Page 1979
4.3.4.1 Using Preformed Iminium Salts......Page 1980
4.3.4.2 Using Iminium Salts Generated In Situ......Page 1982
4.3.5 Reactions with gem-Amino Ethers......Page 1983
4.3.6 References......Page 1986
4.4.1 Introduction......Page 1987
4.4.2 Cyclization with pi-Nucleophiles......Page 1989
4.4.2.1 Carbonyl Compounds......Page 1990
4.4.2.2 Acetals and Enol Ethers......Page 1993
4.4.2.3 Arenes......Page 1996
4.4.2.4 Alkenes......Page 2003
4.4.2.5 Alkynes......Page 2008
4.4.2.6 Organosilanes......Page 2010
4.4.2.7 Relative Reactivities of Intramolecular pi-Nucleophiles......Page 2016
4.4.3 Electron Transfer Induced Photocyclizations......Page 2017
4.4.4 Molecular Rearrangements Terminated by Mannich Cyclizations......Page 2020
4.4.5 References......Page 2024
4.5.1 Introduction......Page 2027
4.5.2.1 Methods to Generate N-Acyliminium Ions......Page 2028
4.5.2.3 Reaction Behavior......Page 2033
4.5.2.4 Reactivity Compared with Other Electrophilic Species......Page 2036
4.5.3.1 Intermolecular Reactions......Page 2037
4.5.3.2 Intramolecular Reactions......Page 2042
4.5.4.1 Intermolecular Reactions......Page 2046
4.5.4.2 Intramolecular Reactions......Page 2049
4.5.5.1 Intermolecular Reactions......Page 2050
4.5.5.2 Intramolecular Reactions......Page 2051
4.5.6.1 Intermolecular Reactions......Page 2054
4.5.6.2 Intramolecular Reactions......Page 2057
4.5.7 References......Page 2060
4.6.1 Introduction and Brief History of Isocyanide Chemistry......Page 2063
4.6.2.1 alpha-Acyloxycarboxamides......Page 2064
4.6.2.3 alpha-Hydroxyalkyltetrazoles......Page 2066
4.6.3.1 General Features, Scope and Limitations......Page 2067
4.6.3.3 Preparative Advantages......Page 2069
4.6.3.5 Stereochemical Course and Reaction Mechanism......Page 2070
4.6.3.6 Side Reactions......Page 2072
4.6.4.1 Peptide Coupling......Page 2074
4.6.4.2 alpha-Amino Acid Derivatives from Achiral Amines......Page 2075
4.6.4.3 Asymmetric Syntheses of alpha-Amino Acid and Peptide Derivatives......Page 2078
4.6.4.4 beta-Lactams......Page 2080
4.6.4.5 Macromolecules......Page 2084
4.6.6 References......Page 2086
Abbreviations......Page 2090
A......Page 2093
B......Page 2095
C......Page 2099
D......Page 2102
E......Page 2105
F......Page 2106
G......Page 2108
H......Page 2110
I......Page 2114
J......Page 2116
K......Page 2117
L......Page 2121
M......Page 2123
N......Page 2128
O......Page 2130
P......Page 2131
R......Page 2134
59299_v02_aindxc.pdf......Page 2135
S......Page 2136
T......Page 2143
U......Page 2145
V......Page 2146
W......Page 2147
Y......Page 2150
Z......Page 2151
A......Page 2152
B......Page 2162
C......Page 2167
D......Page 2173
E......Page 2175
F......Page 2179
G......Page 2180
H......Page 2181
I......Page 2183
59299_v02_sindxb.pdf......Page 2185
K......Page 2187
L......Page 2189
M......Page 2191
N......Page 2194
O......Page 2195
P......Page 2196
R......Page 2203
S......Page 2204
T......Page 2208
V......Page 2212
Z......Page 2213
Front Matter......Page 2215
Table of Contents......Page 2217
Preface......Page 2219
Contributors to Volume 3......Page 2221
Abbreviations......Page 2223
1.1.1 Introduction......Page 2226
1.1.2.1 Regiospecific Alkylations of Unsymmetrical Acyclic and Cyclic Ketones......Page 2228
1.1.2.2 Stereochemistry of Enolate Alkylations......Page 2237
1.1.2.3 Cycloalkylation Reactions of Saturated Ketones......Page 2243
1.1.2.4 Alkylations of Metal Enolates of Saturated Aldehydes......Page 2245
1.1.3 Alkylations of Metal Dienolates of alpha,beta-Unsaturated Ketones......Page 2246
1.1.4 Alkylations via Silyl Enol Ethers and Other Enol Derivatives......Page 2250
1.1.5.1 Regiochemistry and Stereochemistry of Alkylations of Nitrogen Derivatives of Carbonyl Compounds......Page 2253
59299_v03_01_01b.pdf......Page 2258
1.1.5.2 Enantioselective Syntheses via Alkylations......Page 2260
1.1.6.2 Diasteroselective Alkylations of Exocyclic and Endocyclic Enolates of Carboxylic Acid Derivatives......Page 2264
1.1.6.3 Diastereoselective Alkylations of Acyclic Enolates of Carboxylic Acid Derivatives......Page 2267
1.1.6.4 Diastereoselective Alkylations of Acyclic Carboxylic Acid Derivatives Containing Chiral Auxiliary Groups......Page 2269
1.1.6.5 Cycloalkylations of Enolates of Carboxylic Acid Derivatives......Page 2273
1.1.6.6 Alkylations of Dienolates of alpha,beta-Unsaturated Carboxylic Acid Derivatives......Page 2275
1.1.6.7 Asymmetric Synthesis via Alkylations of Anions of Masked Carboxylic Acid Derivatives......Page 2278
1.1.7.1 Alkylations of Monoanions of beta-Dicarbonyl and Related Compounds......Page 2279
1.1.8 References......Page 2283
1.2.1 Introduction......Page 2289
1.2.2.1 Acyclic Systems......Page 2292
1.2.2.2 Heterocyclic Systems......Page 2293
1.2.3.1 Mechanistic Aspects......Page 2296
1.2.3.2 Acyclic Systems......Page 2299
1.2.3.3 Heterocyclic Systems......Page 2300
1.2.4 References......Page 2306
1.3 Alkylations of Sulfur- and Selenium-Containing Carbanions......Page 2308
1.3.1 Introduction......Page 2309
1.3.2.1 Alkylation......Page 2311
1.3.2.2 Synthetically Useful Transformations of Alkylated Sulfides and Selenides......Page 2329
1.3.3.1 Alkylations of 1-Metallo-1,1-Dithioalkanes Bearing Hydrogen and/or Alkyl Groups on Their Carbanionic Center and Their Synthetic Applications......Page 2344
59299_v03_01_03b.pdf......Page 2349
1.3.3.2 Alkylations of 1,1-(Dithio)Allyl- and 1,1-(Dithio)Propargyl-Metals and Their Synthetic Uses......Page 2354
1.3.3.3 Alkylations of Acyl Anion Equivalents Containing at Least One Sulfur or Selenium on Their Carbanionic Center......Page 2357
1.3.4 alpha-Metalloorthothio- and alpha-Metalloorthoseleno-Formates, as Precursors of Esters......Page 2367
1.3.5.1 Reactions Involving Sulfoxides......Page 2370
1.3.5.2 Alkylations of alpha-Metallo-Alkyl and -Vinyl Selenoxides......Page 2380
1.3.6.1 Reactions Involving alpha-Metalloalkyl Sulfones......Page 2381
59299_v03_01_03c.pdf......Page 2388
1.3.6.2 Reactions Involving alpha-Metalloallyl Sulfones......Page 2391
1.3.6.3 Reactions Involving alpha-Metallovinyl Sulfones......Page 2396
1.3.6.4 Reactions Involving alpha-Metallo-alpha-Heterosubstituted Alkyl Sulfones......Page 2397
1.3.7 Alkylation of Sulfur Ylides......Page 2401
1.3.8 Alkylation of Alkyl Sulfonates, Sultones and Sulfonamides......Page 2403
1.3.9 References......Page 2405
1.4.2 Carbanions Stabilized by Oxygen......Page 2415
1.4.2.2 Preparation by Halogen-Metal Exchange......Page 2416
1.4.2.3 Preparation by Tin-Lithium Exchange......Page 2417
1.4.3.1 Allylic and Benzylic alpha-Alkoxy Carbanions......Page 2418
1.4.3.2 alpha-Alkoxy Carbanions from Protected Cyanohydrins......Page 2419
1.4.3.3 alpha-Alkoxy Carbanions Stabilized by Silicon......Page 2420
1.4.4 Carbanions Stabilized by Boron......Page 2421
1.4.6 Carbanions Stabilized by Phosphorus......Page 2422
1.4.7 Carbanions Stabilized by the Halogens......Page 2424
1.4.8 Carbanions Stabilized by Arsenic, Germanium, Tin, Antimony, Lead and Bismuth......Page 2425
1.4.9 References......Page 2426
1.5.1 Introduction......Page 2428
1.5.2.1 Preparation of the Reagents......Page 2429
1.5.2.2 Nature of the Reagents......Page 2431
1.5.2.3 Mechanism of the Reaction......Page 2434
1.5.2.4 Reactions with Organic Substrates......Page 2436
59299_v03_01_05b.pdf......Page 2447
1.5.3 Nickel and Palladium Catalysts......Page 2448
1.5.3.1 Organonickel Catalysis......Page 2449
1.5.3.2 Organopalladium Catalysis......Page 2451
1.5.4 References......Page 2454
1.6.1 Introduction......Page 2461
1.6.2.1 Alkylations of Vinyl and Aryl Grignard Reagents......Page 2462
1.6.2.2 Alkylations of Vinyl- and Aryl-Lithium Species......Page 2467
1.6.2.3 Alkylations of Heteroatom-Substituted Vinyl Carbanions......Page 2472
1.6.2.4 Alkylations of Allene Carbanions......Page 2476
1.6.2.5 Alkylations by an S_N 2' Process......Page 2477
1.6.3 Alkylations with Less Conventional Electrophiles......Page 2478
1.6.4 Alkylations of Vinyl and Aryl Carbanions, RM, Where M is not equal to Li, Mg or Cu......Page 2479
1.6.5 Alkylations of Heteroaromatic Carbanions......Page 2480
1.6.6 Alkylations at sp^2 -Centers Using Epoxides......Page 2482
1.6.7 References......Page 2486
1.7.2 Metallations of Alkynes......Page 2491
1.7.3.1 Alkylations with Alkyl Halides and Sulfates......Page 2492
1.7.3.2 Alkylations with Epoxides......Page 2497
1.7.3.3 Other Alkylation Reactions......Page 2501
1.7.4 Electrophilic Substitution of Haloalkynes......Page 2504
1.7.5.1 Macrolides......Page 2506
1.7.5.2 Sesquiterpenes......Page 2508
1.7.5.3 Leukotrienes and Prostaglandins......Page 2509
1.7.5.4 Non-Natural Products......Page 2510
1.7.6 References......Page 2511
1.8.1 Introduction......Page 2513
1.8.2.1 Alkylating Agents......Page 2514
1.8.2.2 Catalysts......Page 2515
1.8.3 Alkylation of Arenes......Page 2518
1.8.3.1 Alkylation with Alkyl Halides......Page 2519
1.8.3.2 Alkylation with Alkenes......Page 2524
1.8.3.3 Alkylation with Alcohols, Ethers, Esters, Epoxides and Lactones......Page 2529
1.8.3.4 Alkylation with Di- and Poly-Functional Alkylating Agents......Page 2537
1.8.3.5 Haloalkylation......Page 2540
59299_v03_01_08b.pdf......Page 2541
1.8.3.6 Alkylation with Alkanes......Page 2542
1.8.3.7 Cycloalkylation......Page 2543
1.8.3.8 Transalkylation, Isomerization, Disproportionation and Dealkylation......Page 2547
1.8.4 Alkylation of Alkenes......Page 2551
1.8.6 Alkylation of Alkanes......Page 2552
1.8.7 References......Page 2555
1.9.1 Introduction......Page 2560
1.9.2 Initiation of Cyclization......Page 2561
1.9.3 Propagation of Cyclization......Page 2562
1.9.4 Termination of Cyclization......Page 2564
1.9.5.1 Five-Membered Ring Formation......Page 2566
1.9.5.2 Six-Membered Ring Formation......Page 2568
1.9.5.3 Seven-Membered Ring Formation......Page 2576
1.9.6.1 Bicyclo[4.3.0] Ring Formation......Page 2578
1.9.6.2 Bicyclo[4.4.0] Ring Formation......Page 2579
1.9.7 Tri- and Tetra-Cyclizations......Page 2581
1.9.8.1 Aromatic Steroids......Page 2585
1.9.8.2 Nonaromatic Steroids and Related Compounds......Page 2588
1.9.9 Mechanism......Page 2593
1.9.11 References......Page 2594
1.10.1 Introduction......Page 2597
1.10.2.1 Bicyclo[3.3.0]Octane and Bicyclo[3.2.1]Octane Ring Formation......Page 2598
1.10.2.2 Caged Compounds......Page 2600
1.10.2.3 Endocyclic 1,3- and 1,4-Cyclooctadienes......Page 2601
1.10.2.4 Synthesis of Natural Products......Page 2602
1.10.4 Cyclonona-1,5-Dienes......Page 2604
1.10.5.1 Relevance to the Biosynthesis of Polycyclic Sesquiterpenes......Page 2606
1.10.5.2 Cyclodecadienes......Page 2607
1.10.5.3 Cyclodecenols......Page 2611
1.10.5.4 Cyclodecadiene Monoepoxides......Page 2614
1.10.6 Cycloundecenes......Page 2616
1.10.6.1 Humulene......Page 2617
1.10.6.2 Humulene Epoxides......Page 2620
1.10.7 Other Cycloalkenes......Page 2624
1.10.8 References......Page 2625
2.1.1 Introduction and Scope......Page 2630
2.1.2.1 The Classical Wurtz Reaction......Page 2631
2.1.2.2 Organomagnesium-Derived Reagents......Page 2632
2.1.2.3 Organolithium-Derived Reagents......Page 2636
2.1.2.4 Other Organometallic Reagents......Page 2637
2.1.2.5 Formation of Cyclic Systems......Page 2639
2.1.3.1 Preparation, Structure and Experimental Techniques......Page 2640
2.1.3.2 Reactivity Patterns......Page 2641
2.1.3.3 Coupling with sp^3 Carbon Centers......Page 2643
2.1.4 References......Page 2649
2.2 Coupling Reactions between sp^3 and sp^2 Carbon Centers......Page 2652
2.2.2.1 Primary Alkyllithium and Alkylmagnesium Reagents......Page 2653
2.2.2.2 Secondary Alkyl Grignard Reagents......Page 2657
2.2.2.3 Tertiary Alkyl Grignard Reagents......Page 2658
2.2.2.4 Organozinc and Organotin Reagents......Page 2659
2.2.3.1 Enol Ethers, Enol Carboxylates, Enol Phosphates and Enol Sulfonates......Page 2661
2.2.3.2 Alkenyl Sulfides, Sulfones, Selenides and Tellurides......Page 2663
2.2.4 Coupling between C(sp^3 )-Organometallics and Difunctional Alkenes......Page 2665
2.2.5.1 Coupling of Primary Alkyl Grignard Reagents with Aromatic Halides......Page 2667
2.2.5.3 Organozinc and Organotin Reagents......Page 2669
2.2.6 Coupling of C(sp^3 )-Organometallics with Aryl O, S and Se Compounds......Page 2672
2.2.7 Coupling of C(sp^3 )Organometallics with Polyfunctional Aromatics......Page 2674
2.2.8.1 Furans and Thiophenes......Page 2676
2.2.8.2 Pyridines and Quinolines......Page 2677
2.2.8.3 Heteroaromatic Compounds Containing More Than Two Heteroatoms......Page 2678
2.2.9 Coupling of C(sp^3 )-Organometallics with Acyl Chlorides and Related Compounds......Page 2680
2.2.10.1 Coupling between C(sp^2)-Organometallics and Primary Alkyl Halides......Page 2681
2.2.10.3 Coupling between C(sp^2)-Organometallics and C(sp^3)-Oxygen Compounds......Page 2683
2.2.10.4 Coupling of C(sp^2)-Organometallics with Allylic Halides and Related Compounds......Page 2684
2.2.11 References......Page 2694
2.3.1 Introduction......Page 2698
2.3.2.1 Alkene-Alkene Dimerization......Page 2699
2.3.2.2 Crossed Alkene-Alkene Coupling......Page 2701
2.3.2.3 Allene Synthesis by sp^2-sp^2 Coupling......Page 2708
2.3.2.4 Alkene-Aryl Coupling......Page 2709
2.3.2.5 Alkene-Heteroaryl Coupling......Page 2714
2.3.3.1 Aryl-Aryl Dimerization......Page 2716
2.3.3.2 Crossed Aryl-Aryl Coupling......Page 2718
59299_v03_02_03b.pdf......Page 2720
2.3.3.3 Intramolecular Aryl-Aryl Coupling......Page 2722
2.3.4.1 Heteroaryl-Heteroaryl Coupling......Page 2726
2.3.4.2 Aryl-Heteroaryl Coupling......Page 2729
2.3.5 References......Page 2733
2.4.1 Introduction......Page 2738
2.4.2.1 Organocopper Reagents......Page 2739
2.4.3 Palladium- and Nickel-Catalyzed Cross-Coupling Reactions......Page 2740
2.4.3.1 Alkynylzinc Chlorides......Page 2741
2.4.3.2 Alkynylmagnesium Halides......Page 2744
2.4.3.4 Reactions of 1-Alkenyl Metals with 1-Alkynyl Halides......Page 2746
2.4.3.5 Reactions of Terminal Alkynes with sp^2 -Carbon Halides......Page 2747
2.4.3.6 Palladium-Catalyzed Vinylation of Alkynic Iodides......Page 2761
2.4.4 Applications to the Synthesis of Natural Products......Page 2762
2.4.5 References......Page 2765
2.5.1 Introduction......Page 2767
2.5.2 Oxidative Homocoupling Reactions of Terminal Alkynes......Page 2768
2.5.4 Coupling of Organometallic Alkynides with 1-Haloalkynes......Page 2769
2.5.5 Oxidative Coupling Reactions of Organometallic Alkynides......Page 2770
2.5.6.1 Linear Polyalkynes......Page 2771
2.5.6.2 Cyclic Alkynes......Page 2772
2.5.6.3 Polymer Synthesis......Page 2773
2.5.6.4 Natural Product Synthesis......Page 2774
2.5.6.6 Copper-Polymer Complexes as Catalysts for Oxidative Coupling Reactions......Page 2775
2.5.7 References......Page 2776
2.6.1 Introduction......Page 2778
2.6.2.1 Aromatic Carbonyl Compounds......Page 2779
2.6.2.2 Aliphatic Carbonyl Compounds......Page 2785
2.6.3 Intramolecular Couplings......Page 2787
2.6.4 alpha,beta-Unsaturated Carbonyl Compounds......Page 2792
2.6.5.1 Intermolecular Couplings......Page 2794
2.6.5.2 Intramolecular Couplings......Page 2796
2.6.6 Thiocarbonyl Couplings......Page 2797
2.6.7.1 Intermolecular Couplings......Page 2798
2.6.7.2 Intramolecular Couplings......Page 2803
59299_v03_02_06b.pdf......Page 2807
2.6.8 Mixed Couplings......Page 2810
2.6.9 Miscellaneous Couplings......Page 2812
2.6.10 Carbonyl-Alkene Cyclizations......Page 2813
2.6.11 Carbonyl-Alkyne Cyclizations......Page 2817
2.6.12 Carbonyl-Allene Cyclizations......Page 2820
2.6.13 Refrences......Page 2821
2.7.1 The Reduction of Carboxylic Esters by Alkali Metals......Page 2827
2.7.2.1 Heterogeneous Conditions......Page 2828
2.7.3.1 Side Reactions......Page 2829
2.7.3.2 Trapping with Trimethylsilyl Chloride......Page 2830
2.7.4 Acyloin Coupling Reactions with Acyl Chlorides and Acid Anhydrides......Page 2831
2.7.6.1 Acyclic Systems......Page 2832
2.7.6.2 Cyclic Acyloins......Page 2834
2.7.7 Coupling Reactions between Esters and Ketones......Page 2844
2.7.8 References......Page 2845
2.8.1 Introduction and Historical Background......Page 2847
2.8.2 Reaction Conditions for the Kolbe Electrolysis......Page 2848
2.8.3 Mechanism of the Kolbe Electrolysis......Page 2850
2.8.4 Symmetrical Coupling Reactions of Carboxylic Acids......Page 2852
2.8.5 Cross-Coupling Reactions of Different Carboxylic Acids......Page 2856
2.8.6 Addition of Kolbe Radicals to Double Bonds......Page 2860
2.8.7 The Nonkolbe Electrolysis......Page 2863
2.8.9 References......Page 2868
2.9.1.1 General......Page 2873
2.9.1.2 Mechanistic Possibilities......Page 2874
2.9.2.1 Phenol-Phenol C-C Coupling......Page 2877
2.9.2.2 Biaryls Formed in Phenol Ether Couplings......Page 2882
2.9.2.3 Biaryls Formed by Aryl Radical Insertion......Page 2891
2.9.3.1 Spirodienones via Phenol-Phenol C-C Coupling......Page 2893
2.9.3.2 Cyclohexadienones via Phenol Ether Coupling......Page 2897
2.9.4.1 Synthesis of Aryl Ethers......Page 2900
2.9.4.2 Spiroethers......Page 2902
2.9.4.3 Aryl Alkyl Ethers via C-O Coupling......Page 2904
2.9.5 C-C Coupling through Aryl Conjugated Double Bonds......Page 2906
2.9.6.1 Couplings Involving Cycloadditions......Page 2910
2.9.6.2 Coupling at Benzylic Carbon......Page 2912
2.9.6.3 C-N Bond Formation......Page 2913
2.9.7 References......Page 2914
3.1.1 Introduction......Page 2918
3.1.3 Wagner-Meerwein Pathways in Bicyclic Systems......Page 2919
3.1.4 Stereoelectronic Features of the Wagner-Meerwein Rearrangement in Synthesis......Page 2922
3.1.5.1 Syntheses Based on Camphor......Page 2923
3.1.5.2 Ring Expansion Reactions......Page 2926
3.1.5.3 Biomimetic Syntheses......Page 2927
3.1.5.4 Syntheses of the Tetracyclic Diterpenoids......Page 2928
3.1.6 References......Page 2931
3.2.1 Introduction......Page 2933
3.2.2 Mechanistic Features......Page 2934
3.2.3 Applications......Page 2938
3.2.4 References......Page 2943
3.3.2 Stereochemistry of Epoxide Opening......Page 2945
3.3.3 Protic Acid Catalyzed Rearrangements......Page 2946
3.3.4 BF_3 -Induced Rearrangements......Page 2953
3.3.5 Magnesium Halide Catalysis......Page 2966
3.3.6 Lithium Salt Catalysis......Page 2972
3.3.6.1 LiClO_4 Catalysis......Page 2973
3.3.6.2 Lithium Halide Catalysis......Page 2975
3.3.7 Other Catalysts......Page 2981
3.3.8 References......Page 2983
3.4.1.1 Semipinacol Rearrangements......Page 2988
3.4.1.2 Boron Rearrangements......Page 2990
3.4.2.1 Rearrangements of 2-Amino Alcohols......Page 2992
3.4.2.2 Additions of Diazoalkanes to Ketones......Page 2994
3.4.2.3 Rearrangements of 2-Hydroxy Sulfides......Page 2995
3.4.2.4 Rearrangements of 2-Hydroxy Selenides......Page 2997
3.4.2.5 Rearrangements of Halohydrins......Page 2998
3.4.2.6 Rearrangements of 2-Halo Ketones and Acetals......Page 2999
3.4.2.7 Rearrangements of 2-Amino Ketones and 2-Hydroxyimines......Page 3001
3.4.2.8 Rearrangements of 2-Hydroxy Ketones......Page 3002
3.4.2.9 Tandem Cyclization-Semipinacol Rearrangements......Page 3003
3.4.3.1 Rearrangements of Triorganylboranes......Page 3004
3.4.3.2 Rearrangements of Boronic Esters......Page 3007
3.4.3.3 Rearrangements of Tetraorganylboronates......Page 3009
3.4.4 References......Page 3011
3.5.1 Introduction......Page 3013
3.5.2.1 Formation of New C-C Bonds......Page 3014
3.5.2.2 Formation of a New C-O Bond......Page 3022
3.5.3 Extracyclic Bond Migration......Page 3023
3.5.4 Photochemical Aromatization......Page 3025
3.5.5.1 Dienone Aromatization with Bond Cleavage......Page 3026
3.5.5.2 Rearrangements in Dienone Reactions with Nucleophiles......Page 3027
3.5.5.3 Tropolone-Phenol Rearrangements......Page 3028
3.5.6 References......Page 3029
3.6.1 Introduction......Page 3031
3.6.2.1 Benzilic Acid Type Rearrangements......Page 3032
3.6.2.2 The Benzilic Ester Rearrangement......Page 3033
3.6.3.2 Bisaryl alpha-Diketones......Page 3035
3.6.3.3 Quinones......Page 3038
3.6.3.4 1-Alkyl-2-Aryl-1,2-Dicarbonyl Systems......Page 3039
3.6.3.5 Aliphatic and Alicyclic alpha-Diketones......Page 3041
3.6.3.6 Heterocyclic Systems......Page 3044
3.6.4 References......Page 3046
3.7.1 Introduction......Page 3049
3.7.2 Mechanism......Page 3050
3.7.3.1 Acyclic alpha-Halo Ketones......Page 3052
3.7.3.2 alpha-Halocycloalkyl Ketones......Page 3055
3.7.3.3 Monocyclic Halo Ketones......Page 3058
3.7.3.4 Bicyclic Halo Ketones......Page 3061
3.7.3.5 Polycyclic Halo Ketones......Page 3064
3.7.3.6 Miscellaneous......Page 3066
3.7.4 References......Page 3067
3.8.1 Introduction......Page 3070
3.8.4 Reaction Conditions......Page 3071
3.8.5 Compatibility of Functional Groups......Page 3074
3.8.6 Mechanism of the Reaction......Page 3075
3.8.7.1 Replacement of the Halide......Page 3077
3.8.7.2 Replacement of the Sulfone Group......Page 3079
3.8.8.1 Cyclobutenes......Page 3080
3.8.8.2 Cyclopentenes, Cyclopentadienes and Cyclopentenones......Page 3083
3.8.8.3 Cyclohexenes and Phenanthrenes......Page 3085
3.8.8.4 Large Ring Systems......Page 3086
3.8.9 Synthesis of Conjugated Dienes, Enynes and Polyenes......Page 3087
3.8.10 Synthesis of Alkynes......Page 3092
3.8.11 References......Page 3093
3.9.1.1 Historical......Page 3096
3.9.1.2 Preparative Routes to alpha-Diazo Ketones......Page 3097
3.9.2.1 Mechanism......Page 3100
3.9.2.2 Stereochemistry......Page 3101
3.9.2.3 Competing Reactions......Page 3102
3.9.3.1 Homologations and Related Reactions......Page 3106
3.9.3.2 Ring Contractions......Page 3109
3.9.3.3 Cycloaddition Reactions......Page 3114
3.9.3.4 The Vinylogous Wolff Rearrangement......Page 3115
3.9.3.5 Related Reactions......Page 3117
3.9.4 References......Page 3118
3.10.1 Introduction......Page 3122
3.10.2 Definitions......Page 3125
3.10.3.1 Indirect Methods......Page 3127
3.10.3.2 Direct Formation of Ylides......Page 3128
3.10.4.1 Synthetic Applications of the Stevens Rearrangement......Page 3130
3.10.4.2 Transfer of Chirality......Page 3136
3.10.5.1 Introduction......Page 3141
3.10.5.2 Synthetic Applications in Alicyclic Systems......Page 3142
3.10.5.3 Configuration of the Newly Formed Double Bond......Page 3152
59299_v03_03_10b.pdf......Page 3157
3.10.5.4 The Erytho-Threo Ratio......Page 3158
3.10.5.5 Transfer of Configuration......Page 3162
3.10.5.6 Ring Contraction Reactions......Page 3163
3.10.5.7 Ring Expansion Reactions......Page 3166
3.10.5.8 Ylidic Rearrangements Involving Alkynes and Allenes......Page 3172
3.10.5.9 Sommelet-Hauser Rearrangement......Page 3174
Acknowledgements......Page 3180
3.10.7 References......Page 3181
3.11.1.1 Historical Development......Page 3184
3.11.1.2 Rearrangement Pathways......Page 3186
3.11.1.3 Heterologs......Page 3187
3.11.2 1,2-Rearrangements......Page 3188
3.11.3.1 Overview......Page 3190
3.11.3.2 2,3-Rearrangements of Allyl Lithiomethyl Ethers......Page 3191
3.11.3.3 2,3-Wittig Rearrangement of Allyl Propargyl Ethers......Page 3193
3.11.3.4 2,3-Wittig Rearrangement of Allyl Benzyl Ethers......Page 3198
3.11.3.6 2,3-Rearrangement of Diallyl Ethers......Page 3200
3.11.3.7 Tandem and Sequential 2,3-Wittig-3,3-Sigmatropic Rearrangements......Page 3203
3.11.3.8 Rearrangement of alpha-Allyloxy Enolates......Page 3205
3.11.3.10 Cyclic 2,3-Rearrangement - Ring Contractions......Page 3217
3.11.4 References......Page 3222
4.1.1 Introduction......Page 3224
4.1.2 Carbonylation Mechanisms......Page 3225
4.1.2.2 Substitutive Carbonylation......Page 3227
4.1.2.3 Additive Carbonylation......Page 3228
4.1.2.5 Decarbonylation......Page 3229
4.1.3 Formation of Aldehydes......Page 3230
4.1.4 Formation of Ketones......Page 3232
4.1.5 Formation of Carboxylic Acids......Page 3235
4.1.6 Formation of Esters......Page 3237
4.1.7 Formation of Lactones......Page 3240
4.1.8 Formation of Amides......Page 3243
4.1.9 Formation of Lactams and Related N-Heterocycles......Page 3244
4.1.11 Double Carbonylation......Page 3248
4.1.12 Decarbonylation......Page 3249
4.1.13 References......Page 3251
4.2 Carbon-Carbon Bond Formation by C-H Insertion......Page 3253
4.2.2.1 Abstraction-Recombination......Page 3254
4.2.2.3 Metallocarbene Insertion......Page 3255
4.2.3.2 Photochemical......Page 3256
4.2.3.3 Alkylidene Carbenes......Page 3257
4.2.3.4 Alkyl Carbenoids......Page 3259
4.2.4.1 Rhodium-Mediated Cyclization......Page 3264
4.2.4.2 Photochemical Cyclization......Page 3265
4.2.5.2 Alkylidene Carbene: Clovene......Page 3266
4.2.5.3 Rhodium-Mediated C-H Insertion......Page 3267
4.2.7 References......Page 3270
A......Page 3271
B......Page 3273
C......Page 3278
D......Page 3282
E......Page 3285
F......Page 3286
G......Page 3288
H......Page 3291
I......Page 3295
J......Page 3296
K......Page 3297
L......Page 3302
M......Page 3304
N......Page 3310
O......Page 3312
P......Page 3314
R......Page 3317
59299_v03_aindxc.pdf......Page 3318
S......Page 3319
T......Page 3327
U......Page 3330
V......Page 3331
W......Page 3332
Y......Page 3335
Z......Page 3336
A......Page 3338
B......Page 3345
C......Page 3349
D......Page 3358
E......Page 3361
F......Page 3364
G......Page 3365
H......Page 3366
I......Page 3368
K......Page 3370
L......Page 3372
M......Page 3374
N......Page 3376
O......Page 3377
P......Page 3379
R......Page 3384
S......Page 3385
T......Page 3389
U......Page 3391
W......Page 3392
Z......Page 3393
Front Matter......Page 3394
Table of Contents......Page 3396
Preface......Page 3398
Contributors to Volume 4......Page 3400
Abbreviations......Page 3402
1.1.1.1 History......Page 3405
1.1.2.1 Carbon Nucleophiles......Page 3407
1.1.2.2 Heteronucleophiles......Page 3434
1.1.3.1 Carbon Nucleophiles......Page 3445
59299_v04_01_01b.pdf......Page 3449
1.1.3.2 Heteronucleophiles......Page 3451
1.1.4 Allenic pi-Systems......Page 3457
1.1.4.1 Carbon Nucleophiles......Page 3458
1.1.4.2 Heteronucleophiles......Page 3459
1.1.6 References......Page 3462
1.2 Conjugate Additions of Reactive Carbanions to Activated Alkenes and Alkynes......Page 3472
1.2.1 Introduction......Page 3473
1.2.2.1 Additions of Alkyl, Aryl, Alkenyl and Alkynyl Groups......Page 3475
1.2.2.2 Additions of Enolates, Azaenolates and alpha-Nitrile Anions......Page 3502
59299_v04_01_02b.pdf......Page 3512
1.2.2.3 Additions of Acyl Anion Equivalents......Page 3516
1.2.2.4 Additions of alpha-Heteroatom-Stabilized Carbanions (Non-Acyl Anion Equivalents)......Page 3518
1.2.2.5 Additions of Homoenolates or Homoenolate Equivalents......Page 3520
1.2.2.6 Heteroconjugate Additions (Carbometallation)......Page 3523
1.2.3 Annulations and Multiple Conjugate Additions (Tandem Michael Reactions)......Page 3524
1.2.4 Additions to 'Push-Pull' Alkenes......Page 3525
1.2.4.1 Enaminones......Page 3526
1.2.4.2 Nitroenamines......Page 3527
1.2.4.4 beta-Alkoxy-alpha,beta-Unsaturated Esters......Page 3528
1.2.4.5 beta-(Alkylthio)Enones, beta-(Alkylthio)-alpha,beta-Unsaturated Esters and beta-(Alkylthio)Nitroalkenes......Page 3529
1.2.4.7 alpha,alpha-Difluoroalkenes......Page 3530
1.2.5 Additions to Alkynic pi-Systems......Page 3531
1.2.6 Electrochemical Mediated Additions......Page 3532
1.2.7 References......Page 3533
1.3.1 Introduction......Page 3541
1.3.2.1 Additions of Alkyl, Aryl, Alkenyl and Alkynyl Groups......Page 3542
1.3.2.2 Additions of Enol Silyl Ethers and Silyl Ketene Acetals......Page 3560
1.3.2.3 Additions of Acyl Anion Equivalents......Page 3564
1.3.2.4 Additions of Homoenolates......Page 3565
1.3.3 Additions to Alkynic pi-Systems......Page 3566
1.3.4 References......Page 3567
1.4.1 Introduction......Page 3571
1.4.2 Mechanistic Considerations......Page 3572
1.4.3 Stoichiometric versus Catalytic Reagents......Page 3574
1.4.4 Variations in the Reagent......Page 3575
1.4.5 Nontransferable Ligands......Page 3577
1.4.6 Solvent Effects......Page 3580
1.4.8.1 gamma-Alkoxy-alpha,beta-Unsaturated Ketones......Page 3581
1.4.8.3 beta-Substituted-alpha,beta-Unsaturated Ketones......Page 3582
1.4.8.5 Polyalkenic alpha,beta-Unsaturated Carbonyl Compounds......Page 3583
1.4.8.6 alpha,beta-Unsaturated Aldehydes......Page 3585
1.4.8.7 alpha,beta-Unsaturated Esters......Page 3586
1.4.8.8 alpha,beta-Alkynic Carbonyl Compounds......Page 3587
1.4.9 Stereoselectivity......Page 3589
1.4.10 Applications......Page 3593
1.4.11 Concluding Remarks......Page 3597
1.4.12 References......Page 3598
1.5.1 Introduction......Page 3601
1.5.2.1 Additions to Chiral Derivatives of alpha,beta-Unsaturated Carboxylic Acids......Page 3602
1.5.2.2 Additions to Chiral Derivatives of alpha,beta-Unsaturated Aldehydes and Ketones......Page 3610
1.5.2.3 Additions to Chiral Vinylic Sulfur Compounds......Page 3615
1.5.2.4 Additions to alpha,beta-Unsaturated Acyl Ligands Bound to a Chiral Metal Center......Page 3619
1.5.3.1 Reactions of Chiral Enolates......Page 3620
1.5.3.2 Reactions of Chiral Azaenolates and Enamines......Page 3623
59299_v04_01_05b.pdf......Page 3625
1.5.3.3 Reactions of Chiral Sulfinyl and Phosphonyl Anions......Page 3628
1.5.3.4 Reactions of Organocopper Compounds Prepared from Chiral Carbanions......Page 3629
1.5.4.1 Reactions Employing Stoichiometric Amounts of Chiral Ligands or Coordinating Cosolvents......Page 3630
1.5.4.2 Reactions Mediated by Chiral Catalysts......Page 3632
1.5.5 Additions of Noncarbon Nucleophiles......Page 3633
1.5.7 References......Page 3634
1.6 Nucleophilic Addition - Electrophilic Coupling with a Carbanion Intermediate......Page 3639
1.6.1.1 Tandem Vicinal Difunctionalization......Page 3640
1.6.1.2 Historical Background......Page 3641
1.6.2 Mechanism and Stereochemistry......Page 3642
1.6.3.1 Aldehydes and Ketones......Page 3644
1.6.3.2 Esters and Amides......Page 3648
1.6.3.3 Alkynes......Page 3651
1.6.3.4 Other Substrates......Page 3653
1.6.4 The Nucleophile......Page 3655
1.6.4.2 Unstabilized Anions......Page 3656
59299_v04_01_06b.pdf......Page 3659
1.6.4.3 Stabilized Anions......Page 3660
1.6.5 The Electrophile......Page 3661
1.6.5.2 Carbonyl-Containing Electrophiles......Page 3662
1.6.5.3 Michael Acceptors......Page 3663
1.6.6 Sequential Michael Ring Closure Reactions......Page 3664
1.6.7 References......Page 3665
1.7.1 Introduction......Page 3671
1.7.2.2 H-F Addition......Page 3672
1.7.2.3 H-Cl Addition......Page 3674
1.7.2.4 H-Br Addition......Page 3681
1.7.2.5 H-I Addition......Page 3689
1.7.3.2 Aminomercuration - Demercuration......Page 3692
1.7.3.3 Amide Addition......Page 3694
1.7.3.4 Azide Addition......Page 3697
1.7.4.1 H-OH Addition......Page 3699
1.7.4.2 H-O_2 H and H-O_2 R Additions......Page 3707
1.7.4.3 H-OR Addition......Page 3709
1.7.4.4 H-O_2 CR Addition......Page 3714
1.7.5 H-SR Addition......Page 3718
1.7.6 H-SeR Addition......Page 3719
1.7.7 References......Page 3721
1.8.1 Introduction......Page 3730
1.8.2.1 Sulfenyl Halides and Related Compounds......Page 3731
1.8.2.2 Sulfonium Salts......Page 3738
1.8.2.3 Selenenyl Halides, Pseudohalides and Related Compounds......Page 3740
1.8.2.4 Tetravalent Selenium......Page 3743
1.8.2.5 Tellurium Compounds......Page 3744
1.8.3.3 Bromine......Page 3745
1.8.3.4 Iodine......Page 3747
1.8.3.6 Reagents with O-X Bonds......Page 3748
1.8.4.1 Thiocyanogen......Page 3749
1.8.4.2 Halogen Azides......Page 3750
1.8.4.3 Halogen Nitrates......Page 3751
1.8.4.5 Halogen Thiocyanates......Page 3752
1.8.4.6 Haloamides......Page 3756
1.8.5.1 Nitronium Tetrafluoroborate......Page 3757
1.8.6 Electrophilic Boron......Page 3758
1.8.8 References......Page 3760
1.9.1.1 Coverage......Page 3764
1.9.1.2 Synthetic Considerations......Page 3765
1.9.1.3 Mechanistic Considerations......Page 3766
1.9.2.1 Small Rings......Page 3768
1.9.2.2 Five- and Six-Membered Rings......Page 3770
59299_v04_01_09b.pdf......Page 3797
1.9.3 Nitrogen Nucleophiles......Page 3798
1.9.3.2 Five- and Six-Membered Rings......Page 3799
1.9.4 Sulfur Nucleophiles......Page 3814
1.9.5 References......Page 3816
2.1.1 Introduction......Page 3823
2.1.2 Carbon Nucleophiles......Page 3826
2.1.2.1 Organometallics......Page 3827
2.1.2.2 Active Hydrogen Compounds......Page 3829
2.1.3 Nitrogen Nucleophiles......Page 3833
2.1.4 Oxygen Nucleophiles......Page 3837
2.1.5 Sulfur Nucleophiles......Page 3841
2.1.6.1 Hydride......Page 3844
2.1.6.2 Halides......Page 3845
2.1.6.3 Phosphorus Nucleophiles......Page 3846
2.1.7 References......Page 3847
2.2.1 Introduction......Page 3851
2.2.2.1 Mechanistic Considerations......Page 3852
2.2.2.2 Choice of Solvents......Page 3856
2.2.2.3 Nature of the Nucleofuge......Page 3857
2.2.2.4 Nature of the Aromatic Substrate......Page 3858
2.2.3.1 Formation of C-C Bonds, Carbon-Based Nucleophiles......Page 3863
59299_v04_02_02b.pdf......Page 3869
2.2.3.2 Formation of Aryl C-N, C-P, C-As and C-Sb Bonds......Page 3872
2.2.3.3 Formation of Aryl C-O, C-S, C-Se and C-Te Bonds......Page 3874
2.2.4.1 Ring Closure by Intramolecular S_RN 1 Reactions......Page 3876
2.2.4.2 S_RN 1 Reactions Followed by Cyclization......Page 3877
2.2.5 References......Page 3880
2.3.1 Introduction......Page 3883
2.3.2 Generation of Arynes......Page 3885
2.3.2.1 From Aryl Anions......Page 3886
2.3.2.2 From Fragmentation of Cyclic Systems......Page 3888
2.3.2.3 Generation of Substituted Arynes......Page 3889
2.3.3.1 Relative Reactivity of Nucleophiles......Page 3891
2.3.3.2 Regioselectivity in Nucleophilic Addition to Unsymmetrical Arynes......Page 3892
2.3.3.3 Use of Arynic Substitution in Synthesis......Page 3895
2.3.4 References......Page 3913
2.4.1.1 Coverage......Page 3916
2.4.1.2 Relation to Nucleophilic Aromatic Substitution by the S_N Ar Mechanism......Page 3917
2.4.2.1 [(Arene)Cr(CO)_3 ]......Page 3918
2.4.2.2 [(Arene)Mn(CO)_3 ]^ +......Page 3919
2.4.3 Nucleophilic Substitution for Heteroatoms on Arene Ligands, S_N Ar Reaction......Page 3920
2.4.3.1 [(Halobenzene)Cr(CO)_3 ]......Page 3921
2.4.3.2 [(Halobenzene)CpFe]^+......Page 3928
2.4.4.1 Addition-Oxidation: Formal Nucleophilic Substitution for Hydrogen......Page 3930
2.4.4.2 Addition-Protonation: Synthesis of Substituted 1,3-Cyclohexadienes......Page 3941
2.4.4.3 Addition-Acylation......Page 3943
2.4.4.4 Addition to Styrene-Type Ligands Activated by Cr(CO)_3......Page 3945
2.4.5 References......Page 3946
3.1.2 Additions to Alkenes......Page 3949
3.1.2.1 Addition of Oxygen Nucleophiles to Alkenes......Page 3950
3.1.2.2 Addition of Nitrogen Nucleophiles to Alkenes......Page 3957
3.1.2.3 Metal-Catalyzed Allylic Transpositions, Oxy-Cope and Aza-Cope Reactions......Page 3961
3.1.3 Addition of Heteroatom Nucleophiles to Metal-Activated Alkadienes......Page 3963
3.1.4 Addition of Heteroatom Nucleophiles to Metal-Activated Alkynes......Page 3965
3.1.5 References......Page 3966
3.2.2 Alkylation of Monoalkenes......Page 3968
3.2.3 Alkylation of Alkadienes......Page 3977
3.2.4 Alkylation of Alkynes......Page 3979
3.2.5 References......Page 3980
3.3 Nucleophiles with Allyl-Metal Complexes......Page 3981
3.3.1.2 Nature of pi-Allylpalladium-Mediated Functionalization......Page 3982
3.3.2.1 Precursors to pi-Allylpalladium Complexes......Page 3983
3.3.2.2 Range of Nucleophiles Employed in Palladium-Catalyzed Allylic Alkylation......Page 3986
3.3.2.3 Other Reactions of pi-Allylpalladium Complexes......Page 3996
3.3.3.1 Diastereoselectivity and Mechanism......Page 4010
3.3.3.2 Stereochemistry of Addition of Carbon Nucleophiles......Page 4011
3.3.3.3 Stereochemistry of Addition of Oxygen Nucleophiles......Page 4017
3.3.3.4 Stereochemistry of Addition of Amine Nucleophiles......Page 4018
3.3.3.5 Stereochemistry of Addition of Sulfur Nucleophiles......Page 4020
3.3.3.7 Diastereoselectivity of Other Reactions of pi-Allylpalladium Complexes......Page 4021
3.3.4.2 Regioselectivity in the Addition of Soft Carbon Nucleophiles to pi-Allylpalladium Complexes......Page 4023
59299_v04_03_03b.pdf......Page 4025
3.3.4.3 Regioselectivity in the Addition of Enolates to pi-Alylpalladium Complexes......Page 4028
3.3.4.4 Regioselectivity of Organotins......Page 4029
3.3.4.5 Regioselectivity of Organozincs......Page 4030
3.3.4.7 Regioselectivity of Grignards and Organolithiums......Page 4031
3.3.4.8 Regioselectivity of Oxygen Nucleophiles......Page 4033
3.3.4.9 Regioselectivity of Amine Nucleophiles......Page 4034
3.3.4.10 Regioselectivity of Sulfur Nucleophiles......Page 4036
3.3.4.11 Regioselectivity in Other Heteroatom Nucleophiles......Page 4038
3.3.4.12 Regioselectivity in Other pi-Allylpalladium Reactions......Page 4039
3.3.5.2 Chirality Transfer......Page 4045
3.3.5.3 Enantioselectivity with Optically Active Phosphines......Page 4047
3.3.6 References......Page 4050
3.4.1 Introduction......Page 4058
3.4.2.1 Preparation of Substituted Tricarbonylcyclohexadienyliron Complexes......Page 4060
3.4.2.2 Nucleophile Additions to Dienyliron Complexes; General Comments......Page 4065
3.4.2.3 Regiocontrol during Nucleophile Addition to Cyclohexadienyliron Complexes: Applications of Alkoxy- and Methoxycarbonyl-Substituted Complexes in Organic Synthesis......Page 4069
3.4.2.4 Stereocontrol during Nucleophile Addition: Applications in Relative Stereocontrol during Multiple Functionalization of Six- and Seven-Membered Rings......Page 4080
3.4.2.5 Control of Absolute Stereochemistry during Carbon-Carbon Bond Formation Using Dienyliron Complexes......Page 4082
3.4.3.1 Dienylmanganese Complexes......Page 4084
3.4.3.2 Dienylcobalt Complexes......Page 4086
3.4.4 References......Page 4087
3.5.1 Introduction......Page 4090
3.5.2.1 eta^4 -Diene Iron Tricarbonyl Complexes......Page 4092
3.5.2.2 eta^4 -Diene Manganese Tricarbonyl Anions......Page 4097
3.5.3.1 eta^4 -Triene and eta^4 -Tetraene Iron Tricarbonyl Complexes......Page 4101
3.5.4 Summary......Page 4107
3.5.5 References......Page 4108
4.1 Radical Addition Reactions......Page 4110
4.1.2.1 Introduction......Page 4111
4.1.2.2 Transiency of Radicals......Page 4112
4.1.2.3 Structure and Stereochemistry of Radicals......Page 4114
4.1.2.4 General Considerations for the Use of Radical Reactions in Synthesis......Page 4115
4.1.2.6 A Word about Concentrations......Page 4117
4.1.3.1 Chain Reactions......Page 4119
4.1.3.2 Nonchain Reactions......Page 4120
4.1.4.2 Atom and Group Transfer Reactions......Page 4121
4.1.4.3 Addition Reactions......Page 4122
4.1.5 Radicals and Synthetic Planning......Page 4126
4.1.6.1 Chain Methods......Page 4130
59299_v04_04_01b.pdf......Page 4131
4.1.6.2 Nonchain Methods......Page 4153
59299_v04_04_01c.pdf......Page 4156
4.1.7.1 Additions to Other Multiple Bonds......Page 4160
4.1.7.2 Additions to Aromatic Rings......Page 4161
4.1.8 Additions of Heteroatom-Centered Radicals......Page 4165
4.1.10 References and Notes......Page 4167
4.2 Radical Cyclizations and Sequential Radical Reactions......Page 4173
4.2.1 Introduction......Page 4174
4.2.1.1 Hexenyl Radical Cyclizations......Page 4175
4.2.1.2 Butenyl, Pentenyl, Heptenyl and Other Radical Cyclizations......Page 4179
4.2.1.3 Stereoselectivity......Page 4181
4.2.2 Cyclizations of Carbon-Centered Radicals to Carbon-Carbon Multiple Bonds......Page 4183
4.2.2.1 Chain Methods......Page 4184
4.2.2.2 Nonchain Methods......Page 4199
59299_v04_04_02b.pdf......Page 4200
4.2.3 Cyclizations of Carbon-Centered Radicals to Aromatic Rings......Page 4203
4.2.4.1 Nitrogen-Centered Radicals......Page 4205
4.2.4.2 Oxygen-Centered Radicals......Page 4206
4.2.5.2 Carbon-Oxygen Multiple Bonds......Page 4209
4.2.6.1 Simple Sequences......Page 4212
4.2.6.2 Tandem (and Higher) Sequences......Page 4213
4.2.8 References......Page 4221
4.3 Vinyl Substitutions with Organopalladium Intermediates......Page 4226
4.3.1.1 Basic Reaction......Page 4227
4.3.2 Vinyl Substitution with Arenes and Heterocycles......Page 4228
4.3.2.3 Reaction Scope and Conditions......Page 4229
4.3.3 Vinyl Substitution with Cyclopalladated Complexes......Page 4230
4.3.4.1 Organomercury Compounds......Page 4231
4.3.4.2 Silanes and Silyl Enol Ethers......Page 4233
4.3.4.4 Vinyl Substitution with Other Organometal and Nonmetal Derivatives......Page 4234
4.3.5.1 Vinyl Substitution with Alkyl, Aryl and Vinyl Halides......Page 4235
4.3.5.3 Vinyl Substitutions with Carboxylic Acid Halides, Aryl Sulfinates and Arylsulfonyl Chlorides......Page 4249
4.3.5.4 Vinyl Substitution with Triflate Esters and Related Esters......Page 4251
4.3.6 References......Page 4255
4.4 Carbometallation of Alkenes and Alkynes......Page 4257
4.4.1 Introduction......Page 4258
4.4.2.2 The Carbolithiation of Alkenes and Dienes......Page 4259
4.4.2.3 The Carbolithiation of Alkynes......Page 4264
4.4.3.1 General Consideration......Page 4265
4.4.3.2 The Carbomagnesiation of Alkenes......Page 4266
4.4.3.3 The Carbomagnesiation of Alkynes......Page 4269
4.4.4.1 General Considerations......Page 4271
4.4.4.2 The Carbozincation of Alkenes......Page 4272
4.4.4.3 The Carbozincation of Alkynes......Page 4275
4.4.5.1 General Considerations......Page 4276
4.4.5.2 The Carboboration of Alkenes......Page 4277
4.4.5.3 The Carboboration of Alkynes......Page 4278
4.4.6.2 The Carboalumination of Alkenes......Page 4279
4.4.6.3 The Carboalumination of Alkynes......Page 4280
4.4.7.1 General Considerations......Page 4285
59299_v04_04_04b.pdf......Page 4286
4.4.7.2 The Carbocupration of Alkenes, 1,2- and 1,3-Dienes......Page 4287
4.4.7.3 The Carbocupration of Alkynes......Page 4288
4.4.7.4 Synthetic Applications of Alkenylcopper Organometallics......Page 4293
4.4.8.2 Addition to Alkenes and Dienes......Page 4295
4.4.8.3 Addition to Alkynes......Page 4297
4.4.9 References......Page 4299
4.5.1 Introduction......Page 4304
4.5.2 Hydroformylation......Page 4305
4.5.2.2 Mechanisms......Page 4306
4.5.2.3 Regio- and Stereo-Chemistry......Page 4307
4.5.2.4 Hydroformylation of Unfunctionalized Alkenes......Page 4310
4.5.2.5 Hydroformylation of Functionalized Alkenes......Page 4313
4.5.2.6 Asymmetric Hydroformylation......Page 4318
4.5.3 Carboxylation......Page 4323
4.5.3.1 Mechanisms......Page 4327
4.5.3.3 Hydrocarboxylation of Alkenes......Page 4330
4.5.3.4 Alkenes and Alkynes Containing Functional Groups......Page 4332
4.5.3.6 Asymmetric Hydrocarboxylation......Page 4336
4.5.4.1 Mechanisms......Page 4337
4.5.4.2 Dicarboxylation of Alkenes......Page 4338
4.5.5 References......Page 4340
4.6.1.1 Scope of Chapter......Page 4342
4.6.1.2 Stereochemical Definitions......Page 4343
4.6.2.1 Thermal Reactions......Page 4344
4.6.2.3 Metal-Catalyzed Reactions......Page 4345
4.6.4 Use of Geminal Dihaloalkanes and Related Compounds......Page 4352
4.6.4.2 Related Procedures......Page 4359
4.6.5 Use of Transition Metal Carbene Complexes......Page 4367
4.6.6.1 Use of Ylides......Page 4377
4.6.7 Conclusion......Page 4378
4.6.8 References......Page 4385
4.7.1 Introduction......Page 4389
4.7.2.1 Methods for the Generation of Dihalocarbenes......Page 4390
4.7.2.2 Addition of Dihalocarbenes to pi-Bonds......Page 4392
4.7.3.1 Reductive Dehalogenation......Page 4396
4.7.3.2 Lithium-Halogen Exchange and the Chemistry of 1-Lithio-1-Halocyclopropanes......Page 4397
4.7.3.3 Doering-Moore-Skattebøl Allene Synthesis......Page 4399
4.7.3.4 Skattebøl Rearrangement......Page 4402
4.7.3.5 Other Carbenoid Reactions......Page 4403
4.7.3.6 Elimination and Elimination-Addition......Page 4404
4.7.3.7 Electrocyclic Ring Opening......Page 4406
4.7.3.9 Formation of Heterocycles......Page 4411
4.7.3.10 Miscellaneous Reactions......Page 4413
4.7.5 References......Page 4415
4.8.1 Introduction......Page 4420
4.8.2 Generation of Ketocarbenoids......Page 4421
4.8.3 Classes of Ketocarbenoids......Page 4422
4.8.4.1 Intermolecular Reactions......Page 4423
4.8.4.2 Intramolecular Reactions......Page 4429
4.8.4.3 Further Transformations of Cyclopropanes......Page 4432
4.8.5 Addition of Ketocarbenoids to Alkynes......Page 4439
4.8.6.1 Benzenes......Page 4441
4.8.6.2 Furans......Page 4447
4.8.6.3 Pyrroles......Page 4450
4.8.6.4 Thiophenes......Page 4452
4.8.8 References......Page 4453
4.9.1 Introduction......Page 4457
4.9.3 Mechanistic Considerations......Page 4458
4.9.3.1 Stepwise Mechanism......Page 4460
4.9.5 Nonconcerted Cycloadditions......Page 4461
4.9.5.1 [4 + 3] Cycloaddition......Page 4463
4.9.6.1 Nitrones......Page 4464
4.9.6.2 Nitrile Oxides......Page 4466
4.9.6.3 Nitrile Ylides......Page 4469
4.9.6.4 Nitrilimines......Page 4471
4.9.6.5 Azomethine Ylides......Page 4473
4.9.6.6 Carbonyl Ylides......Page 4477
4.9.6.7 Thiocarbonyl Ylides......Page 4481
4.9.6.8 Azomethine Imines......Page 4483
4.9.6.9 Mesoionic Ring Systems......Page 4484
4.9.6.10 Ozone......Page 4486
4.9.6.11 Azides......Page 4487
4.9.6.12 Diazoalkanes......Page 4489
4.9.7 Conclusion......Page 4492
4.9.8 References......Page 4493
4.10 Intramolecular 1,3-Dipolar Cycloadditions......Page 4498
4.10.1 Introduction......Page 4499
4.10.2.2 Open-Chain Alkenylnitrones......Page 4500
4.10.2.3 Cyclic Alkenylnitrones......Page 4504
4.10.2.4 Oxime Cyclization Reactions......Page 4507
4.10.2.5 Tandem Michael-Nitrone Cyclization Reactions......Page 4508
4.10.2.6 Tandem Diels-Alder-Nitronic Ester Cydization Reactions......Page 4509
4.10.3.1 General......Page 4511
4.10.3.2 Open-Chain Alkenyl Nitrile Oxides......Page 4512
4.10.3.3 Cyclic Alkenyl Nitrile Oxides......Page 4514
4.10.3.4 Tandem Reaction Sequences Involving Nitrile Oxide Cyclizations......Page 4519
4.10.3.5 Alkynyl Nitrile Oxides......Page 4520
4.10.4.2 Alkenyl Azomethine Ylides......Page 4521
4.10.4.4 Munchnones......Page 4524
4.10.4.5 Alkynyl and Allenyl Azomethine Ylides......Page 4526
4.10.5.1 General......Page 4528
4.10.5.2 Alkenyl Nitrile Ylides......Page 4529
59299_v04_04_10b.pdf......Page 4530
4.10.6.1 General......Page 4531
4.10.6.2 Alkenyl Azomethine Imines......Page 4533
4.10.6.3 Alkynyl Azomethine Imines......Page 4534
4.10.6.4 Hydrazone Cyclization Reactions......Page 4535
4.10.6.6 Tandem Sydnone Intermolecular-Intramolecular Cycloadditions......Page 4536
4.10.7.2 Alkenyl Nitrile Imines......Page 4537
4.10.8.2 Cyclization of Diazoalkenes......Page 4538
4.10.8.5 Acid-Catalyzed Cyclization of Tosylhydrazones......Page 4543
4.10.9.2 Azidoalkenes......Page 4544
4.10.9.3 Azidoalkynes......Page 4545
4.10.10.1 General......Page 4546
4.10.10.2 Open-Chain Carbonyl Ylide-Alkene Cyclizations......Page 4548
4.10.10.3 Cyclic Carbonyl Ylide-Alkene Cyclizations......Page 4549
4.10.11 Thiocarbonyl Ylide Cyclizations......Page 4550
4.10.12 Nitrile Sulfide Cyclizations......Page 4552
4.10.13 References......Page 4553
A......Page 4556
B......Page 4558
C......Page 4564
D......Page 4569
E......Page 4572
F......Page 4573
G......Page 4575
H......Page 4579
I......Page 4583
J......Page 4585
K......Page 4586
L......Page 4591
M......Page 4594
N......Page 4601
O......Page 4603
P......Page 4605
R......Page 4608
59299_v04_aindxc.pdf......Page 4610
S......Page 4612
T......Page 4620
V......Page 4624
W......Page 4626
Y......Page 4629
Z......Page 4630
A......Page 4632
B......Page 4640
C......Page 4644
D......Page 4652
E......Page 4655
F......Page 4657
H......Page 4658
I......Page 4660
59299_v04_sindxb.pdf......Page 4662
K......Page 4663
L......Page 4664
M......Page 4665
N......Page 4667
O......Page 4669
P......Page 4672
Q......Page 4677
R......Page 4678
S......Page 4679
T......Page 4682
V......Page 4685
Z......Page 4686
Front Matter......Page 4687
Table of Contents......Page 4689
Preface......Page 4692
Contributors to Volume 5......Page 4694
Abbreviations......Page 4697
1.1.1 Introduction......Page 4700
1.1.2.1 Electron Deficient Alkenes as Enophiles......Page 4701
1.1.2.2 Electron Deficient Alkynes as Enophiles......Page 4705
1.1.3 Intramolecular Reactions: Alkenes as the Ene Component......Page 4708
1.1.3.1 Formation of 1-Vinyl-2-Alkylcyclopentanes from 1,6-Dienes......Page 4709
1.1.3.2 Formation of 1-Vinyl-2-Alkylidinecyclopentanes from 1,6-Enynes......Page 4714
1.1.3.3 Formation of 1-Vinyl-2-Alkylcyclohexanes from 1,7-Dienes......Page 4716
1.1.3.4 Formation of 1-Vinyl-2-Alkylidinecyclohexanes from 1,7-Enynes......Page 4717
1.1.3.5 Miscellaneous Reactions......Page 4718
1.1.4 Intramolecular Reactions: Enols as the Ene Component; 'The Conia Reaction'......Page 4719
1.1.5 Addendum......Page 4723
1.1.6 References......Page 4724
1.2.1 Introduction......Page 4727
1.2.2.1 Magnesium-Ene Reactions......Page 4728
1.2.2.2 Zinc- and Aluminum-Ene Reactions......Page 4729
1.2.2.3 Boron-Ene Reactions......Page 4731
1.2.2.4 Palladium- and Nickel-Ene Reactions......Page 4733
1.2.3.2 Intramolecular Magnesium-, Zinc- and Lithium-Ene Reactions......Page 4735
1.2.3.3 Intramolecular Palladium- and Nickel-Ene Reactions......Page 4744
1.2.4 Summary......Page 4757
1.2.5 References......Page 4758
2.1.2 Dimerizations of Alkenes via 1,4-Diradicals......Page 4760
2.1.3 Intramolecular and Mixed [2 + 2] Cycloadditions......Page 4764
2.1.4 Diradical versus Zwitterionic Intermediates......Page 4769
2.1.6 References......Page 4776
2.2.1 Introduction......Page 4782
2.2.2.1 Chemo- and Regio-Selectivity......Page 4783
2.2.2.2 Stereoselectivity......Page 4784
2.2.3 2-Thietanones from Ketenes and Thiocarbonyl Compounds......Page 4786
2.2.4.1 Direct Combination of Ketenes with Imines......Page 4787
2.2.4.2 Reactions with Ketene Precursors......Page 4789
2.2.4.3 Cycloadditions of Ketenes to Carbodiimides......Page 4796
2.2.5 2-Azetidinones from Enolates or Enol Ethers and Imines......Page 4797
2.2.6.1 Scope......Page 4799
2.2.6.2 Stereochemical Aspects......Page 4804
2.2.7.1 Scope......Page 4805
2.2.7.2 Stereochemistry......Page 4808
2.2.8.1 2-Iminoazetidines from Ketenimines and C=N Bonds......Page 4810
2.2.8.3 2-Iminothietanes from Ketenimines and C=S Bonds......Page 4811
2.2.9 Cycloadditions of Thioketenes......Page 4812
2.2.10 Four-Membered Heterocycles from Activated Alkynes and C=X Bonds......Page 4813
2.2.11 Miscellaneous......Page 4814
2.2.12 References......Page 4815
2.3.1 Introduction......Page 4820
2.3.2 Mechanism......Page 4821
2.3.3.1 Regiochemical Control......Page 4822
2.3.3.2 Stereochemical Control......Page 4825
2.3.3.3 Enantioselectivity......Page 4829
2.3.4.1 Regioselectivity......Page 4830
2.3.4.2 Stereoselectivity......Page 4834
2.3.5 Unactivated Alkenes......Page 4842
2.3.6 Copper Catalyzed [2 + 2] Photocycloadditions......Page 4844
2.3.7 References......Page 4845
2.4.1 Introduction......Page 4848
2.4.2 Mechanistic Considerations......Page 4849
2.4.3 Photochemical Synthesis Using Alkenyl and Alkynyl Addends......Page 4854
2.4.4 Paterno-Büchi Reaction of Dienyl and Allenyl Systems......Page 4862
2.4.5 The Furan-Carbonyl Photocycloaddition......Page 4865
59299_v05_02_04b.pdf......Page 4874
2.4.6 The Intramolecular Paterno-Büchi Photocycloaddition......Page 4875
2.4.7 Excited-State Asymmetric Synthesis Using the Paterno-Büchi Photocycloaddition......Page 4880
Acknowledgements......Page 4884
2.4.9 References......Page 4885
2.5 Di-pi-Methane Photoisomerizations......Page 4890
2.5.1.2 Nomenclature......Page 4891
2.5.2.1 Acyclic 1,4-Dienes......Page 4892
2.5.2.3 Polycyclic Dienes......Page 4893
2.5.2.4 Benzo and Dibenzo Systems......Page 4894
2.5.2.5 Cyclopropyl-pi-Methane Rearrangements......Page 4895
2.5.2.6 Hetera-Substituted Systems......Page 4896
2.5.3.1 General Aspects......Page 4899
2.5.3.2 Divinyl versus Benzo-Vinyl Bridging......Page 4900
2.5.3.3 Independent Generation of the Diradical Intermediates......Page 4901
2.5.4.1 Chemoselectivity......Page 4903
2.5.4.2 Regioselectivity......Page 4906
2.5.4.3 Stereoselectivity......Page 4907
2.5.5 Synthetic Utility......Page 4908
2.5.6 Practical Aspects......Page 4909
2.5.7 References......Page 4910
2.6.1 Introduction......Page 4912
2.6.2.1 Correlation of Excited States and Reactivity......Page 4913
2.6.2.2 Selective Population of Excited States: The Clue to Reaction Selectivity......Page 4915
2.6.3 Classes of ODPM-Reactive Substrates......Page 4916
2.6.3.1 Acyclic beta,gamma-Unsaturated Carbonyls......Page 4917
2.6.3.2 Semicyclic beta,gamma-Unsaturated Carbonyls......Page 4918
2.6.3.3 Mono-, Bi- and Spiro-Cyclic beta,gamma-Unsaturated Ketones......Page 4919
2.6.3.4 Bridged beta,gamma-Enones......Page 4921
2.6.4.2 Bridged Bicyclic beta,gamma-Enones......Page 4925
2.6.5 Applications in Natural Product Synthesis......Page 4926
2.6.6 References......Page 4932
3.1.1 Introduction......Page 4935
3.1.2.1 Regioselectivity......Page 4936
3.1.2.2 Stereoselectivity (Intramolecular)......Page 4938
3.1.3.1 Palladium Trimethylenemethane Complex [(eta^3 -TMM)PdL_2 ]......Page 4940
3.1.3.2 Organo-Tin and -Zinc Reagents Derived from 3-Iodo-2-[(Trimethylsilyl)Methyl]Propene......Page 4942
3.1.4.1 Regioselectivity......Page 4943
3.1.4.2 Stereoselectivity......Page 4950
3.1.5.1 Polarized Cyclopropanes......Page 4962
3.1.6 References......Page 4965
3.2.1 General Introduction......Page 4967
3.2.3.1 Allylic Precursors......Page 4968
3.2.3.3 Allenylic Precursors......Page 4973
3.2.3.4 Cyclopropyl Precursors......Page 4977
3.2.4 The 2-Oxyallyl Synthons......Page 4978
3.2.4.1 Cyclopentanone and Cyclopentenone Syntheses......Page 4979
3.2.4.3 Intramolecular Reactions......Page 4982
3.2.5 The Trimethylenemethane Synthons......Page 4983
3.2.5.1 TMM from Methylenecyclopropanes......Page 4984
3.2.5.2 TMM from Bifunctional Conjunctive Reagents......Page 4994
59299_v05_03_02b.pdf......Page 4995
3.2.5.3 TMM Cycloaddition in Natural Product Synthesis......Page 5004
3.2.6 References......Page 5008
4.1 Intermolecular Diels-Alder Reactions......Page 5011
4.1.1.2 Reactivity......Page 5012
4.1.1.3 Regiochemistry......Page 5013
4.1.1.4 Stereochemistry......Page 5014
4.1.2.1 Nitroalkenes......Page 5016
4.1.2.2 Enamines and Enamides......Page 5018
4.1.2.3 Alkenyl Sulfur Derivatives......Page 5020
4.1.2.4 Alkenyl Halogen Derivatives......Page 5023
4.1.3 Heteroatom-Substituted Dienes......Page 5024
4.1.3.1 Oxygen-Substituted Dienes......Page 5025
4.1.3.2 Nitrogen-Substituted Dienes......Page 5027
4.1.3.3 Sulfur-Substituted Dienes......Page 5029
4.1.3.4 Silicon-, Tin- and Boron-Substituted Dienes......Page 5031
4.1.3.5 2-[(Silyl-, Stannyl- and Thio-)Methyl]-1,3-Dienes......Page 5033
4.1.4.1 Lewis Acids......Page 5035
4.1.4.2 Medium Effects......Page 5037
4.1.5.1 Induction by a Prochiral Center: 5-Substituted Cyclopentadienes......Page 5043
4.1.5.2 Induction by Resident Stereocenter(s)......Page 5044
4.1.6.1 Background......Page 5048
4.1.6.2 Covalently Bound Auxiliary Groups......Page 5049
4.1.6.3 Chiral Catalysts......Page 5072
59299_v05_04_01c.pdf......Page 5073
4.1.7.1 Background and Preparation......Page 5075
4.1.7.2 Reactions with Cyclopentadiene and Furan Derivatives......Page 5076
4.1.7.3 Reactions with Benzenes and Anthracenes......Page 5079
4.1.7.5 3,4-Pyridyne as a Dienophile......Page 5080
4.1.8.1 Background......Page 5081
4.1.8.2 Preparation......Page 5082
4.1.8.3 Regio- and Stereo-Chemistry......Page 5086
4.1.8.4 Applications in Synthesis......Page 5089
4.1.9 References......Page 5092
4.2 Heterodienophile Additions to Dienes......Page 5096
4.2.2.1 N-Sulfonyl Imines......Page 5097
4.2.2.2 N-Acyl Imines......Page 5099
4.2.2.3 C-Acyl Imines......Page 5103
4.2.2.4 Alkyl and Aryl Imines and Immonium Salts......Page 5104
4.2.2.5 Cycloadditions with Heterocyclic Azadienes......Page 5106
4.2.2.6 Oximino Dienophiles......Page 5107
4.2.2.8 Intramolecular Cycloadditions......Page 5108
4.2.3 Nitriles......Page 5111
4.2.4.1 Aryl Nitroso Compounds......Page 5112
4.2.4.2 alpha-Chloro Nitroso Compounds......Page 5113
4.2.4.3 Acyl Nitroso Compounds......Page 5114
4.2.4.4 Cyano and Sulfonyl Nitroso Compounds......Page 5116
4.2.6 N-Sulfinyl Dienophiles......Page 5117
4.2.6.1 Monoimines......Page 5118
4.2.6.3 Bis-Imines......Page 5120
4.2.7 Azo Dienophiles......Page 5121
4.2.7.1 Acyclic Azo Systems......Page 5123
4.2.7.2 Cyclic Azo Systems......Page 5124
4.2.8 Carbonyl Dienophiles......Page 5125
4.2.8.1 Electron-Deficient Aldehydes......Page 5126
4.2.8.2 Electron-Deficient Ketones......Page 5127
4.2.8.3 Aliphatic and Aromatic Aldehydes......Page 5128
4.2.8.4 Cycloadditions with Highly Oxygenated Dienes......Page 5129
4.2.9 Thiocarbonyl Dienophiles......Page 5130
4.2.9.2 Thioaldehydes......Page 5131
4.2.9.3 Thioesters, Dithioesters and Related Compounds......Page 5133
4.2.9.5 Thienium Salts and Related Cations......Page 5134
4.2.9.6 Sulfines and Sulfenes......Page 5135
4.2.10 Selenocarbonyl Dienophiles......Page 5137
4.2.12 References......Page 5139
4.3.1 Introduction......Page 5145
4.3.2.1 1-Oxa-1,3-Butadienes......Page 5147
4.3.2.2 Electron-Deficient 1-Oxa-1,3-Butadienes......Page 5152
4.3.2.4 Intramolecular 1-Oxabutadiene Diels-Alder Reactions......Page 5158
4.3.2.6 Hetero 1-Oxabutadienes......Page 5162
4.3.3 Thiabutadienes......Page 5163
4.3.4 Azabutadienes......Page 5164
4.3.4.1 1-Aza-1,3-Butadienes......Page 5167
4.3.4.2 2-Aza-1,3-Butadienes......Page 5174
4.3.4.3 Hetero 2-Aza-1,3-Butadienes......Page 5179
4.3.4.7 1,4-Diaza-1,3-Butadienes......Page 5180
59299_v05_04_03b.pdf......Page 5181
4.3.5.2 Six-Membered Ring Heteroaromatic Azadienes......Page 5185
4.3.6.1 Cationic Azadienes......Page 5186
4.3.6.2 Cationic Oxabutadienes......Page 5195
4.3.6.3 Cationic Thiabutadienes......Page 5198
4.3.7 References......Page 5201
4.4.1 Introduction......Page 5207
4.4.2.1 All-Carbon Nona- and Deca-Trienes......Page 5209
4.4.2.2 Heteroatom-Substituted Nona- and Deca-Trienes......Page 5221
4.4.3 Relative Diastereoselection......Page 5226
4.4.3.1 Trienes with Saturated Connecting Chains......Page 5227
59299_v05_04_04b.pdf......Page 5229
4.4.3.2 Decatrienones and Other Trienes with Unsaturated Connecting Chains: Intervention of Boat-like Transition States......Page 5233
4.4.4 Asymmetric Intramolecular Diels-Alder Reactions......Page 5237
Acknowledgements......Page 5239
4.4.5 References......Page 5240
4.5 Retrograde Diels-Alder Reactions......Page 5245
4.5.1 Introduction......Page 5246
4.5.2.2 alpha,beta-Unsaturated Aldehydes and Ketones......Page 5247
4.5.2.3 Acyclic Allylic Alcohols......Page 5248
4.5.2.4 alpha,beta-Unsaturated Thio Compounds......Page 5250
4.5.2.6 Vinyl Alcohols, Ethers and Esters......Page 5251
4.5.2.8 Enamines......Page 5252
4.5.2.11 Endocyclic Alkenes......Page 5254
4.5.3.1 Substituted Acyclic Butadienes......Page 5259
4.5.3.3 Extrusion of Molecular Nitrogen......Page 5261
4.5.3.4 Cyclobutadiene and Cyclopentadienes......Page 5262
4.5.3.5 Cyclohexadiene Derivatives......Page 5263
4.5.3.6 Benzene and Benzene Derivatives......Page 5265
4.5.4.1 Acyclic Aldehydes, Ketones and Carboxylic Esters......Page 5267
4.5.4.2 Thio Analogs......Page 5269
4.5.4.3 Nitrogen Analogs......Page 5270
4.5.5.1 Oxygen Heterocyclics Generated by Ethylene Formation......Page 5271
4.5.5.2 Oxygen Heterocyclics Generated by Butadiene Formation......Page 5273
4.5.5.4 Nitrogen Heterocyclics Generated by Butadiene Formation......Page 5275
4.5.5.5 Six-Membered Nitrogen Heterocyclics......Page 5277
4.5.6.1 Cyclic Compounds......Page 5278
4.5.6.3 Solvolysis Reactions......Page 5279
4.5.6.4 Acyclic Species......Page 5280
4.5.7.1 Silenes, Disilenes and Silanones......Page 5281
4.5.7.2 o-Xylylene via Retro-Dimetalla-DA Reaction......Page 5282
4.5.8 References......Page 5283
5.1.1 Introduction......Page 5287
5.1.2.1 beta-Heteroatom-Substituted Allylic Cations......Page 5288
5.1.2.2 Other Allylic Cations......Page 5291
5.1.2.3 Singlet Vinylcarbenes and Vinylcarbenoids......Page 5293
5.1.2.4 Miscellaneous Methods......Page 5294
5.1.3 Reactions with Dienes......Page 5295
5.1.3.2 Cyclic 1,3-Dienes......Page 5297
5.1.3.3 Heterocycles......Page 5299
5.1.4 Synthetic Applications......Page 5302
5.1.4.3 Tropane Alkaloids......Page 5303
5.1.4.5 Nonactic Acid, Lilac Alcohol and Prelog-Djerassi Lactone......Page 5305
5.1.4.8 Thromboxane A_2 and B_2......Page 5306
5.1.5 References......Page 5307
5.2.1 Introduction......Page 5310
5.2.2.1 2,4,6-Cycloheptatrien-1-One (Tropone) as the 6pi Addend......Page 5311
5.2.2.2 Fulvenes as 6pi Addends......Page 5319
5.2.2.3 Cyclic Trienes as 6pi Addends......Page 5325
5.2.3.1 Photocycloaddition Reactions of 1,3-Dienes and Arene Substrates......Page 5328
5.2.3.2 Dimerization of o-Xylylene and 2,3-Dimethylenefurans......Page 5331
5.2.3.3 Applications of 'Indirect' [4 + 4] Cycloadditions to Synthesis......Page 5332
5.2.4 References......Page 5335
5.3.1 Introduction......Page 5337
5.3.2 Historical Perspective......Page 5338
5.3.3 Mechanistic Considerations......Page 5340
5.3.4 Summary of Mechanism and Reaction Selectivity......Page 5346
5.3.6 Synthetic Applications......Page 5349
5.3.7 References......Page 5363
6.1.1 Introduction......Page 5366
6.1.2 Preparation of Cyclobutenes......Page 5367
6.1.3.1 Substituent Effects on the Cyclobutene Ring Opening Reaction......Page 5369
6.1.4.1 Preparation of Reactive 1,3-Dienes......Page 5374
6.1.4.2 Two-Carbon Ring Expansion via Cyclobutene Ring Openings......Page 5377
6.1.5 Cyclobutenone Ring Openings......Page 5379
6.1.6 Benzocyclobutenes and Derivatives......Page 5382
6.1.7 References......Page 5385
6.2.1.1 Scope......Page 5389
6.2.1.2 Historical Perspective......Page 5390
6.2.1.3 Theoretical Treatment of Electrocyclic Processes: Stereochemistry......Page 5393
6.2.2.1 General Considerations Including Acyclic Hexatrienes and Selected Ring Fused Systems......Page 5396
6.2.2.2 Cyclic and Annulated Hexatrienes......Page 5401
59299_v05_06_02b.pdf......Page 5419
6.2.3.1 Ketenes......Page 5420
6.2.3.2 Allenes......Page 5424
6.2.3.3 Alkynes......Page 5425
6.2.4.1 Retro Electrocyclizations: Triene Syntheses......Page 5427
6.2.4.2 Heterocyclic Applications......Page 5430
6.2.4.3 Higher-Order Electrocyclic Processes......Page 5433
Acknowledgement......Page 5434
6.2.5 References......Page 5435
6.3 Nazarov and Related Cationic Cyclizations......Page 5441
6.3.1.1 Historical Background......Page 5442
6.3.1.2 Organization and Scope......Page 5443
6.3.2.1 Mechanism and Stereospecificity......Page 5444
6.3.3 Cyclization of Divinyl and Allyl Vinyl Ketones......Page 5445
6.3.3.2 Monocyclic Precursors......Page 5447
6.3.3.3 Biscyclic Precursors......Page 5448
6.3.3.5 Anomalous Cyclizations......Page 5449
6.3.3.6 Photochemical Cyclizations......Page 5450
6.3.4 Silicon-Directed Nazarov Cyclizations of Divinyl Ketones (SDNC)......Page 5451
6.3.4.1 Acyclic Precursors......Page 5452
6.3.4.3 Monocyclic Precursors (Chiral)......Page 5453
6.3.4.5 Tin-Directed Nazarov Cyclizations (TDNC)......Page 5455
6.3.5.2 Cyclization of Divinyl Ketones from alpha'-Hydroxy Enones......Page 5456
6.3.5.4 Cyclization of Divinyl Ketones from Alkynic Alcohols......Page 5457
6.3.6.1 Solvolysis of Geminal Dichlorides......Page 5460
6.3.6.2 Solvolysis of 2-Furylcarbinols......Page 5461
6.3.6.3 Solvolysis of Vinylallenes and Derivatives......Page 5462
6.3.7.1 Aliphatic Acid Halides......Page 5465
6.3.7.3 Alkenic Esters......Page 5466
6.3.7.4 Alkenic Acid Chlorides and Bromides......Page 5467
6.3.8 Applications in Synthesis......Page 5469
6.3.9 References......Page 5471
7.1 Cope, Oxy-Cope and Anionic Oxy-Cope Rearrangements......Page 5475
7.1.1.1 Oxy-Cope Rearrangement......Page 5476
7.1.1.2 Anionic Oxy-Cope Rearrangement......Page 5478
7.1.2.2 Conjugating Substituents......Page 5479
7.1.2.3 Aromatization of Cope Products......Page 5480
7.1.2.4 Ring Strain......Page 5481
7.1.2.5 Conformational Factors......Page 5484
7.1.2.6 Irreversibility of Oxy-Cope Rearrangements......Page 5485
7.1.3.2 Allenes......Page 5487
7.1.4.2 Catalysis......Page 5488
7.1.5.1 1, 2-Divinylcyclopropanes......Page 5493
7.1.5.2 1,2-Divinylcyclobutanes......Page 5495
7.1.5.3 1,2-Divinylcyclopentanes......Page 5496
7.1.5.4 1,2-Divinylcyclohexanes......Page 5499
7.1.5.6 1,2-Divinylcyclooctanes and Larger Rings......Page 5500
7.1.6.1 Vinylbicycloalkenes......Page 5502
7.1.6.2 2-Exo-Methylene-6-Vinylbicyclo[2.2.2]Octanes......Page 5505
7.1.6.3 Bridged 1,5-Cyclooctadienes......Page 5506
7.1.6.4 Double Diastereoselection with Chiral Vinyl Substituents......Page 5507
7.1.6.5 Tricyclic Skeletons......Page 5508
7.1.7.1 Transition State Conformation......Page 5509
7.1.7.4 Transfer of Chirality......Page 5511
7.1.8 Conclusions......Page 5512
7.1.9 References......Page 5513
7.2.1 Introduction......Page 5517
7.2.2.2 Methods of Preparation of Allyl Vinyl Ethers......Page 5520
7.2.2.3 The Claisen Rearrangement of Allyl Vinyl Ethers......Page 5522
7.2.2.5 The Carroll Rearrangement......Page 5524
7.2.2.6 The Eschenmoser Amide Acetal Rearrangement......Page 5526
7.2.2.7 The Johnson Ortho Ester Rearrangement......Page 5529
7.2.2.8 The Ireland Silyl Ester Enolate Rearrangement......Page 5530
7.2.2.9 Charge-Accelerated Claisen Rearrangements......Page 5537
7.2.2.11 Competitive Rearrangements......Page 5540
7.2.2.12 Solvent Effects......Page 5544
7.2.3 Enzymatic Claisen Rearrangements......Page 5545
7.2.4.1 Kinetics......Page 5546
7.2.4.2 Transition State Structures......Page 5547
7.2.4.3 Elements of Stereocontrol......Page 5549
7.2.6 References......Page 5556
7.3.1 Introduction......Page 5564
7.3.2.1 [3,3]-[3,3] Rearrangements......Page 5565
7.3.2.2 [2,3]-[3,3] Rearrangements......Page 5577
7.3.2.3 Sulfur-Based Rearrangements......Page 5578
7.3.3.1 Linear Processes......Page 5580
7.3.3.2 Ring-Forming Processes......Page 5583
7.3.4 References......Page 5586
8.1.1 Introduction......Page 5588
8.1.2.1 Bonding and Energetics of Cyclopropane Systems......Page 5589
8.1.2.2 Reactive Tendencies......Page 5590
8.1.2.3 Guide to Preparation......Page 5593
8.1.3 Rearrangements of Vinylcyclopropanes......Page 5594
8.1.3.1 [1,5] Shift Pathways......Page 5595
8.1.3.2 Vinylcyclopropane-Cyclopentene Rearrangement......Page 5596
8.1.3.3 Ring Expansions of Oxyvinylcyclopropanes......Page 5608
8.1.3.4 Reactions with Nucleophiles (Normal and Vinylogous Modes)......Page 5610
8.1.3.5 Radical Reactions or Cycloadditions......Page 5615
8.1.4 Rearrangements of Vinyloxiranes......Page 5617
8.1.4.1 Thermal Isomerization......Page 5618
8.1.4.2 Nucleophilic Opening......Page 5620
59299_v05_08_01b.pdf......Page 5624
8.1.5 Rearrangements of Vinylaziridines......Page 5626
8.1.6 Cyclopropyl-Carbonyls and -Imines......Page 5630
8.1.7 Miscellaneous Systems......Page 5636
8.1.8 Survey of General Methodologies......Page 5640
8.1.9 Survey of Total Syntheses......Page 5641
8.1.11 References......Page 5654
8.2.1 Introduction......Page 5660
8.2.2.1 Rearrangement Pathways......Page 5661
8.2.3.2 Enantiospecificity......Page 5662
8.2.3.3 Synthesis of Functionalized Cycloheptanes......Page 5665
8.2.4.1 Synthesis of Functionalized Bicyclo[5.n.0]Alkanes and Related Substances......Page 5668
8.2.4.2 Natural Product Syntheses......Page 5671
8.2.5.1 Background......Page 5673
8.2.5.2 Synthesis of Substituted Bicyclo[3.2.1]Octa-2,6-Dienes......Page 5674
8.2.5.3 Natural Product Syntheses......Page 5677
8.2.6 7-(1-Alkenyl)Bicyclo[4.1.0]Hept-2-Enes......Page 5680
8.2.7.1 Synthesis of Tricyclic Substances Containing the Bicyclo[3,2,1]Octane Carbon Skeleton......Page 5682
8.2.7.2 Natural Product Synthesis......Page 5683
8.2.8 References......Page 5686
8.3.1.1 Introduction......Page 5688
8.3.1.2 Azaanion- and Oxyanion-Accelerated Rearrangements......Page 5689
8.3.1.3 Carbanion-Accelerated Rearrangements......Page 5693
8.3.2.1 Introduction......Page 5695
8.3.2.2 Oxyanion-Accelerated Vinylcyclopropane Rearrangements......Page 5696
8.3.2.3 Carbanion-Accelerated Vinylcyclopropane Rearrangements......Page 5701
8.3.2.4 Carbocation-Accelerated Vinylcyclopropane Rearrangements......Page 5703
8.3.3.1 Vinylcyclobutane Rearrangements......Page 5705
59299_v05_08_03b.pdf......Page 5709
8.3.3.2 Divinylcyclobutane Rearrangements......Page 5713
8.3.3.3 Cyclobutene Rearrangements......Page 5719
8.3.4 References......Page 5722
9.1.1.1 Introduction......Page 5725
9.1.1.2 Scope of the Reaction......Page 5726
9.1.2 Mechanism: Regio- and Diastereo-Selectivity......Page 5727
9.1.3.1 Reactions Involving Acyclic Alkenes: Chemo-, Regio- and Diastereo-Selectivity......Page 5731
9.1.3.2 Reactions Involving Monocyclic and Fused Bicyclic Alkenes: Chemo- and Regio-Selectivity......Page 5734
9.1.3.3 Reactions Involving Bridged Bicyclic Alkenes: Regio- and Diastereo-Selectivity......Page 5737
9.1.3.4 Synthetic Applications......Page 5739
9.1.4.1 Reactions Involving Acyclic All-Carbon Enynes......Page 5741
9.1.4.2 Reactions Involving Acyclic Heteroatom-Containing Enynes......Page 5743
9.1.4.3 Reactions Involving Cyclic Enynes......Page 5745
9.1.4.4 Synthetic Applications......Page 5748
9.1.5 References......Page 5750
9.2.1 Introduction......Page 5753
9.2.2.1 [2 + 2] Cycloadditions......Page 5755
9.2.2.3 [4 + 2] Cycloadditions......Page 5758
9.2.2.5 Coupling of Anions of the Carbene Ligand with C-X sigma-Bonds......Page 5763
9.2.2.6 Coupling of Anions of the Carbene Ligand with C-X pi-Bonds......Page 5764
9.2.2.7 Michael Additions to alpha,eta-Unsaturated Carbene Complexes......Page 5769
9.2.2.8 Nucleophilic Substitutions at and Cleavage of the Carbene Ligand......Page 5771
9.2.3.1 Coupling of the Carbene Ligand with Alkenes and 1,3-Dienes......Page 5772
9.2.3.2 Coupling of the Carbene Ligand with Alkynes......Page 5777
59299_v05_09_02b.pdf......Page 5779
9.2.3.3 Coupling of the Carbene Ligand with Cumulenes and C-X pi-Bonds......Page 5795
9.2.4 References......Page 5798
9.3.2 Reactions between Carbon-Carbon Double Bonds......Page 5802
9.3.2.1 Industrial Applications......Page 5803
9.3.2.2 Fine Chemical Synthesis......Page 5804
9.3.2.4 Synthesis of Macrocycles......Page 5805
9.3.2.5 Polymer Applications......Page 5807
9.3.3.1 Titanium Based Reagents......Page 5809
9.3.3.2 Other Transition Metal Based Reagents......Page 5812
9.3.5 References......Page 5813
9.4.1 Introduction......Page 5815
9.4.2.2 Cyclopentanones: Regio- and Diastereo-Selectivity......Page 5816
9.4.2.3 Cyclopentenones and Related Compounds: Chemo-, Regio- and Diastereo-Selectivity......Page 5817
9.4.2.4 Cyclopentadienones and Related Compounds: Chemo- and Regio-Selectivity......Page 5819
9.4.3.2 Furanones: Regioselectivity......Page 5822
9.4.3.3 Furandiones......Page 5824
9.4.3.4 Thiophenes, Selenophenes and Similar Heterocycles: Regioselectivity......Page 5825
9.4.3.5 Pyrroles and Related Compounds......Page 5826
9.4.4.1 Cyclohexanes and Cyclohexenes: Regioselectivity......Page 5827
9.4.4.2 Cyclohexadienes: Regio- and Diastereo-Selectivity......Page 5828
9.4.4.3 Benzenes: Chemo- and Regio-Selectivity......Page 5830
59299_v05_09_04b.pdf......Page 5836
9.4.5.1 Pyridines: Chemo- and Regio-Selectivity......Page 5838
9.4.5.2 Pyridones and Related Compounds: Chemo- and Regio-Selectivity......Page 5841
9.4.5.3 Pyrones and Similar Heterocycles: Chemo- and Regio-Selectivity......Page 5843
9.4.6 References......Page 5844
9.5.1 Introduction......Page 5849
9.5.2.1 Zirconium-Promoted Bicyclization and Reactions of Zirconabicycles......Page 5851
9.5.2.2 Synthetic Applications of the Zirconium-Promoted Bicyclization of Enynes......Page 5852
9.5.2.3 Bicyclization Promoted by Other Group IV Metals......Page 5855
9.5.3 Diyne Bicyclization......Page 5857
9.5.4 Diene Bicyclization......Page 5858
9.5.5.1 Formation of Zirconacyclopropenes and Zirconacyclopropanes......Page 5859
9.5.5.2 Formation of Zirconacyclopentadienes, Zirconacyclopentenes and Zirconacyclopentanes via Three-Membered Zirconacycles......Page 5864
9.5.6 Conclusion......Page 5868
9.5.7 References......Page 5869
9.6.2 Transition Metal Catalyzed Reactions of Bicyclo[1.1.0]Butanes: Synthesis of Allylcyclopropanes......Page 5871
9.6.3 Transition Metal Catalyzed Reactions of Bicyclo[2.1.0]Pentanes: Synthesis of Bicyclo[2.2.1]Heptanes......Page 5872
9.6.4 Transition Metal Catalyzed Reactions of Other Strained Polycyclic Hydrocarbons......Page 5873
9.6.5 Transition Metal Catalyzed Reactions of Methylenecyclopropanes: Synthesis of Methylenecyclopentanes......Page 5874
9.6.6 Transition Metal Catalyzed Reactions of Cyclopropenes: Synthesis of Vinylcyclopropanes......Page 5883
9.6.9 Transition Metal Catalyzed Reaction of Cyclopropenones......Page 5886
9.6.10 Transition Metal Catalyzed Reactions of Cyclobutenediones: Synthesis of Quinones......Page 5888
9.6.11 References......Page 5890
A......Page 5892
B......Page 5894
C......Page 5899
D......Page 5903
E......Page 5906
F......Page 5907
G......Page 5909
H......Page 5912
I......Page 5916
J......Page 5917
K......Page 5918
L......Page 5923
M......Page 5926
N......Page 5931
O......Page 5933
P......Page 5934
R......Page 5937
S......Page 5940
T......Page 5947
V......Page 5951
W......Page 5952
Z......Page 5956
A......Page 5958
B......Page 5964
C......Page 5970
D......Page 5982
E......Page 5986
F......Page 5989
G......Page 5990
H......Page 5991
I......Page 5993
J......Page 5995
K......Page 5996
L......Page 5997
M......Page 5998
N......Page 5999
O......Page 6001
P......Page 6003
Q......Page 6009
S......Page 6010
T......Page 6013
U......Page 6016
Y......Page 6017
Z......Page 6018
Front Matter......Page 6019
Table of Contents......Page 6021
Preface......Page 6023
Contributors to Volume 6......Page 6025
Abbreviations......Page 6027
1.1.1 Introduction......Page 6030
1.1.2.1 Substitution of Alkyl Halides......Page 6031
1.1.2.2 Deamination of Amines via Diazonium Salts......Page 6032
1.1.2.3 Oxirane Ring Opening by Carbon Nucleophiles......Page 6033
1.1.2.4 Rearrangement Reactions Leading to Alcohols......Page 6043
1.1.2.5 Inversion of Alcohols......Page 6047
1.1.3.1 Cyclic and Acyclic Ethers......Page 6051
1.1.3.2 Epoxides......Page 6054
1.1.4 References......Page 6057
1.2.1 Introduction......Page 6061
1.2.2 The Fischer-Helferich Method......Page 6063
1.2.3.2 The Koenigs-Knorr Method: Bromide and Chloride as Leaving Groups......Page 6065
1.2.3.4 Sulfur as Leaving Group......Page 6074
1.2.3.5 Anhydro Sugars as Glycosyl Donors......Page 6076
1.2.4.1 Introduction and Earlier Examples of Oxygen Activation......Page 6077
1.2.4.2 The Trichloroacetimidate Method: Derivation of New Principles for Glycoside Synthesis; Trichloroacetimidate Formation......Page 6078
1.2.4.3 The Trichloroacetimidate Method: Application to Glycoside and Saccharide Synthesis......Page 6079
1.2.5 The Anomeric O-Alkylation Method......Page 6082
1.2.7 Glycosides and Saccharides of 2-Deoxy Sugars......Page 6087
1.2.8 References......Page 6089
1.3.2.1 Alkylation of Amines by Alkyl Halides......Page 6093
1.3.3.2 Alkylation of Amines by Sulfonates and Other Activated Alcohols......Page 6100
1.3.2.3 Manipulation of Amino Group Equivalents......Page 6104
1.3.3 Reaction of pi-Allyl Complexes with Nitrogen Nucleophiles......Page 6113
1.3.4.1 Epoxides......Page 6116
1.3.4.2 Aziridines......Page 6121
1.3.5 References......Page 6126
1.4 Synthesis of Nitroso, Nitro and Related Compounds......Page 6130
1.4.2.1 Aliphatic Nitro Compounds......Page 6131
1.4.2.2 Aromatic Nitro Compounds......Page 6137
1.4.3.1 Carbon-Heteroatom Linkage with Nucleophilic Heteroatoms......Page 6138
1.4.3.2 Carbon-Nitrogen Linkage via Electrophilic Amination......Page 6142
1.4.4.1 Carbon-Nitrogen Linkage with Nucleophilic Nitrogen......Page 6143
1.4.4.2 Carbon-Nitrogen Linkage via Electrophilic Amination......Page 6145
1.4.4.3 Nitrogen-Nitrogen Linkage......Page 6146
1.4.5.2 Diazomethane......Page 6147
1.4.5.5 Aryldiazoalkanes......Page 6148
1.4.6.1 Acyclic alpha-Diazo Ketones......Page 6149
1.4.6.2 Cyclic alpha-Diazo Ketones......Page 6150
1.4.6.3 alpha-Diazo Esters......Page 6151
1.4.6.4 Diazo Transfer to Active Methylene Compounds......Page 6152
1.4.7.2 Alkene Insertion to Make Cyclopropanes......Page 6153
1.4.7.5 Hetero-H Insertion......Page 6154
1.4.7.7 Elimination to Make Alkenes......Page 6155
1.4.8 References......Page 6156
1.5.1 Introduction......Page 6160
1.5.2.1 Thioacetals......Page 6161
1.5.2.2 Other Sulfides......Page 6165
1.5.3 Sulfoxides......Page 6175
1.5.4 Sulfones......Page 6184
1.5.5 Conclusion......Page 6193
1.5.6 References......Page 6194
1.6.1.1 Synthesis from Tertiary Phosphines and Various Compounds......Page 6198
1.6.1.2 From Phosphonium Salts......Page 6200
1.6.1.3 From Conversion of Other Phosphonium Ylides......Page 6204
1.6.2.2 Vinylidenephosphoranes......Page 6223
1.6.3 References......Page 6225
1.7.1 Nucleophilic Halogenation......Page 6230
1.7.2.1 Chlorination of Alkyl Alcohols......Page 6231
1.7.2.2 Chlorination of Alkyl Alcohol Derivatives......Page 6233
1.7.2.4 Chlorination of Diazo Ketones......Page 6234
1.7.2.6 Other Chlorinations......Page 6235
1.7.3.1 Bromination of Alkyl Alcohols......Page 6236
1.7.3.2 Bromination of Alkyl Alcohol Derivatives......Page 6237
1.7.3.5 Bromination of Diazonium Salts......Page 6238
1.7.3.6 Other Brominations......Page 6239
1.7.4.1 Iodination of Alkyl Alcohols......Page 6240
1.7.4.3 Iodination of Ethers and Epoxides......Page 6241
1.7.4.5 Iodination of Diazonium Salts......Page 6242
1.7.5.1 Fluorination of Alkyl Alcohols......Page 6243
1.7.5.2 Fluorination of Alkyl Alcohol Derivatives......Page 6245
1.7.5.4 Fluorination of Diazo Ketones......Page 6246
1.7.5.6 Other Fluorinations......Page 6247
1.7.6 References......Page 6248
1.8.1.1 Introduction......Page 6251
1.8.1.2 By Replacement of a Halogen Substituent......Page 6252
1.8.1.3 Exchange of Oxygen or Sulfur Functionality......Page 6260
1.8.1.4 Exchange of Other Nitrogen Functionality......Page 6265
1.8.1.5 Exchange of a Hydrogen......Page 6266
1.8.1.6 Nitriles from Organometallic Compounds......Page 6267
1.8.2 Isonitriles......Page 6268
1.8.3 Cyanates......Page 6269
1.8.4.2 Azides from Halogen, Sulfonate and Sulfate Derivatives......Page 6271
1.8.4.3 Azides by Exchange of Oxygen or Sulfur Functionality......Page 6278
1.8.4.4 Azides by Exchange of Nitrogen Functionality......Page 6280
1.8.5 References......Page 6282
1.9.1.1 Reaction Mechanism......Page 6286
1.9.1.2 Reaction Conditions......Page 6288
1.9.1.3 The Nitrile Component......Page 6290
1.9.1.4 The Carbenium Ion Source......Page 6292
1.9.2.1 Intramolecular Cyclization of the Nitrilium Ion......Page 6297
1.9.2.2 Intramolecular Formation of the Nitrilium Ion......Page 6303
1.9.3.1 Physical Techniques......Page 6305
1.9.3.2 Metallic Reagents......Page 6308
59299_v06_01_09b.pdf......Page 6310
1.9.3.3 Generation of Onium Intermediates......Page 6312
1.9.4.1 Relationship of Ritter and Other Reactions......Page 6316
1.9.4.2 Isonitriles and Ritter-Type Processes......Page 6318
1.9.5 References......Page 6321
2.1.1 Introduction......Page 6326
2.1.2.1 Acid Halides from Carboxylic Acids......Page 6327
2.1.2.2 Acid Halides from Acid Halides by Transformation......Page 6331
2.1.2.4 Acid Halides from Carboxylic Acid Esters......Page 6332
2.1.2.7 Acid Halides by Introduction of a Halocarbonyl Group......Page 6333
2.1.3.1 Acid Anhydrides from Carboxylic Acids by Dehydration......Page 6334
2.1.3.2 Acid Anhydrides from Carboxylic Acid Salts and Acid Halides......Page 6339
2.1.3.3 Acid Anhydrides by Miscellaneous Methods......Page 6340
2.1.4 alpha-Ketonitriles......Page 6341
2.1.4.1 alpha-Ketonitriles from Acid Halides......Page 6342
2.1.5 References......Page 6343
2.2 Synthesis of Esters, Activated Esters and Lactones......Page 6347
2.2.1.2 Synthesis of Esters by Acyl Transfer to Alcohols (Carboxy Group Activation, CGA)......Page 6348
2.2.1.3 Esters from Carboxylic Acids and Alcohols via Hydroxy Group Activation (HGA)......Page 6357
2.2.1.4 CGA and HGA Esterifications at Will: The DCC Method......Page 6358
2.2.1.5 Alkylative Esterification......Page 6359
2.2.1.6 Selective Monoacylation of Polyols......Page 6361
2.2.1.7 Transesterifications......Page 6363
2.2.1.8 Enzymatic Acylations and Deacylations......Page 6364
2.2.2.2 Synthesis of beta-Lactones......Page 6366
2.2.2.3 Synthesis of gamma-Lactones......Page 6374
59299_v06_02_02b.pdf......Page 6381
2.2.2.4 Synthesis of delta-Lactones......Page 6389
2.2.2.5 Enantioselective Lactonization......Page 6391
2.2.2.6 Macrolactonization......Page 6392
2.2.3 References......Page 6400
2.3.1 Amides......Page 6405
2.3.1.1 Carboxylic Acids and Amines......Page 6406
2.3.1.2 Alkylation and Arylation of Amides......Page 6423
2.3.1.3 Nitriles......Page 6424
2.3.1.5 Reduction......Page 6426
2.3.1.6 Thioamides......Page 6427
2.3.1.7 Rearrangements......Page 6428
59299_v06_02_03b.pdf......Page 6429
2.3.1.8 Construction of the Carbon Frame......Page 6430
2.3.2.1 Intramolecular Acylation of Amino Acid Derivatives......Page 6431
2.3.2.3 Construction of the Carbon Frame......Page 6432
2.3.3 Imides......Page 6433
2.3.4 References......Page 6435
2.4.1 Introduction......Page 6442
2.4.2.1 Thioacylation with O-Alkyl Thiocarboxylates......Page 6443
2.4.2.3 Thioacylation with Dithiocarboxylic Acids......Page 6444
2.4.2.4 Thioacylation with Thioacyl Chlorides......Page 6445
2.4.2.5 Thioacylation with Dithiocarboxylates......Page 6446
2.4.2.6 Thioacylation with Thioamides......Page 6447
2.4.2.7 Thioacylation with Thioketenes or Thioketene Equivalents......Page 6449
2.4.3.1 Thiolysis of Imidoyl Chlorides......Page 6451
2.4.3.2 Thiolysis of Imidates......Page 6452
2.4.3.4 Thiolysis of Nitriles......Page 6453
2.4.5 References......Page 6455
2.5.1 Introduction......Page 6458
2.5.2.1 Acylation of Thiols with Carboxylic Acids......Page 6460
2.5.2.2 Acylation of Thiols with Acyl Halides......Page 6463
2.5.2.3 Acylation of Thiols with Anhydrides, Ketenes and Esters......Page 6466
2.5.2.4 Acylation of Water (Hydrolysis) with Imidothioates, Thioorthoesters and Ketene S,S-Acetals......Page 6467
2.5.2.5 Acylation of Arenes and Carbanions under Formation of Carbon-Carbon Bonds......Page 6468
2.5.3 Thioxoesters and Thioxolactones......Page 6469
2.5.3.1 Thioacylation of Alcohols and Phenols with Thioacyl Halides......Page 6471
2.5.3.2 Thioacylation of Alcohols and Phenols with Anhydrides, Thioketenes, Thioesters and Dithioesters......Page 6472
2.5.3.3 Acylation of Hydrogen Sulfide (Sulfhydrolysis) with Imidates and Orthoesters......Page 6473
2.5.4.1 Thioacylation of Thiols with Thioacyl Halides, Thioacyl Anhydrides and Thioketenes......Page 6476
2.5.4.2 Transesterification of Thiols......Page 6477
2.5.4.3 Acylation of Hydrogen Sulfide (Sulfhydrolysis) with Imidothioates and Related Compounds......Page 6478
2.5.4.4 Dithiocarboxylation of Arenes and Carbanions under Formation of Carbon-Carbon Bonds......Page 6479
2.5.5 References......Page 6480
2.6.1 Introduction......Page 6484
2.6.2.1 Preparation......Page 6485
2.6.2.2 Reactions......Page 6491
2.6.3.1 Preparation......Page 6495
2.6.3.2 Reactions......Page 6497
2.6.4.1 Preparation......Page 6499
2.6.4.2 Reactions......Page 6504
2.6.5 References......Page 6505
2.7 Synthesis of Iminium Salts, Orthoesters and Related Compounds......Page 6508
2.7.2.1 Adducts from Amides (Thioamides) and Acylating Reagents......Page 6510
2.7.2.2 Halomethyleneiminium Salts (Amide Halides)......Page 6518
2.7.2.3 Alkoxymethyleneiminium Salts......Page 6524
2.7.2.4 Alkylmercaptomethyleneiminium Salts......Page 6531
2.7.2.5 Amidinium Salts (Aminomethyleneiminium Salts)......Page 6535
2.7.3.1 Imidoyl Halides......Page 6546
59299_v06_02_07b.pdf......Page 6550
2.7.3.2 Imidates (Imidic Acid Esters, Imido Esters, Imidoates)......Page 6552
2.7.3.3 Thioimidates......Page 6559
2.7.3.4 Amidines......Page 6565
2.7.4.1 Carboxylic Orthoesters......Page 6579
2.7.4.2 2,2-Bis(Dialkoxy)Carbonitriles......Page 6587
2.7.4.3 Amide Acetals (Including Lactam Acetals)......Page 6589
2.7.4.4 2-Alkoxy-2-Dialkylaminocarbonitriles......Page 6596
2.7.4.5 Aminal Esters (Bis(Dialkylamino)Alkoxyalkanes)......Page 6597
2.7.4.6 2,2-Bis(Dialkylamino)Carbonitriles......Page 6600
2.7.4.7 Tris(Dialkylamino)Alkanes......Page 6602
59299_v06_02_07c.pdf......Page 6603
2.7.5 References......Page 6606
2.8.1 Introduction......Page 6623
2.8.2.1 Halophosphates......Page 6624
2.8.2.2 Phosphoric-Arenesulfonic Anhydrides......Page 6625
2.8.2.3 Pyrophosphates......Page 6627
2.8.2.4 Acyl Phosphates......Page 6629
2.8.2.5 Phosphoryl Phenoxides and Related Compounds......Page 6630
2.8.2.6 Vinyl Phosphates and Related Compounds......Page 6633
2.8.2.8 Phosphorothioates......Page 6636
2.8.2.10 Miscellaneous......Page 6637
2.8.3.1 Phosphorochloridites (Chloroalkoxyphosphines) and Related Compounds......Page 6638
2.8.4.1 (RO)POX_2 -Type Reagents......Page 6640
2.8.4.2 (RO)PX_2 -Type Reagents......Page 6641
2.8.4.4 (RO)PXY-Type Reagents......Page 6642
2.8.5 Protecting Groups of Phosphoric Acid......Page 6643
2.8.5.1 Aryl Groups......Page 6644
2.8.5.2 Alkyl Groups......Page 6646
2.8.5.3 Miscellaneous......Page 6648
2.8.6 References......Page 6649
3.1.1 Principal Demands for and on Functional Group Protection......Page 6653
3.1.2.1 Urethane Protecting Groups......Page 6657
3.1.2.2 Acyl Protecting Groups......Page 6664
3.1.2.3 Alkyl and Alkylidene Protecting Groups......Page 6666
3.1.2.4 Special Amino-Protecting Groups......Page 6667
3.1.3 Alcohol-Protecting Groups......Page 6668
3.1.3.1 Ether and Acyclic Acetal Protecting Groups......Page 6669
3.1.3.2 Silyl Protecting Groups......Page 6674
59299_v06_03_01b.pdf......Page 6678
3.1.3.3 Ester and Carbonate Protecting Groups......Page 6679
3.1.3.4 Protecting Groups for 1,2- and 1,3-Diols......Page 6681
3.1.4 Thiol-Protecting Groups......Page 6686
3.1.5.1 Ester Protecting Groups......Page 6687
3.1.5.2 Polymer Esters as Protecting and Anchoring Groups......Page 6692
3.1.5.3 Amide Protecting Groups......Page 6694
3.1.5.4 Protection of Carboxylic Groups in Organometallic Transformations......Page 6695
3.1.6.1 Acyclic and Cyclic Acetals and Ketals......Page 6697
3.1.6.2 Acyclic and Cyclic Dithioacetals and Dithioketals......Page 6699
3.1.6.3 O-Substituted Cyanohydrins......Page 6703
3.1.6.4 Substituted Hydrazones and Oximes......Page 6704
3.1.7 Protection of Alkenes and Alkynes......Page 6706
3.1.7.1 Protection of Alkenes......Page 6707
3.1.7.2 Protection of 1,3-Dienes......Page 6712
3.1.7.3 Protection of Alkynes......Page 6714
3.1.8 References......Page 6715
4.1.1 Introduction......Page 6724
4.1.2.1 Formation......Page 6726
4.1.2.2 Structure and Chemical Properties......Page 6728
4.1.2.3 Spectral Properties......Page 6732
4.1.2.4 General Reactions......Page 6734
4.1.2.5 Stereochemical Features......Page 6737
4.1.3.1 Formation......Page 6740
4.1.3.2 Structure and Chemical Properties......Page 6744
4.1.3.4 General Reactions......Page 6745
4.1.3.5 Stereochemical Features......Page 6746
4.1.4.1 Formation......Page 6747
4.1.4.4 General Reactions......Page 6748
4.1.4.5 Stereochemical Features......Page 6749
4.1.5 References......Page 6750
4.2.1 Introduction......Page 6754
4.2.2.1 Reactions Involving Imines or Iminium Ions......Page 6755
4.2.3.2 Reactions Involving Acyliminium Ions......Page 6765
4.3.2.3 Reactions Involving Oxocarbenium Ions......Page 6770
4.2.2.4 Reactions Involving Thiocarbenium Ions......Page 6774
4.2.3.2 By Radical Attack......Page 6776
4.2.4.1 [4 + 2] Cycloadditions (Hetero Diels-Alder Reactions)......Page 6777
4.3.4.2 [2 + 2] Cycloaddition Reactions......Page 6780
4.2.6 References......Page 6781
4.3.1.1 Synthetic Utility of the Beckmann Rearrangement......Page 6784
4.3.1.2 Trapping of the Beckmann Intermediate with Heteroatoms......Page 6787
4.3.1.3 Beckmann Rearrangement - Alkylation Sequence......Page 6790
4.3.1.4 Beckmann Rearrangement - Cyclization Sequence......Page 6792
4.3.1.5 Beckmann Fragmentations......Page 6794
4.3.2.1 Protic Bamford-Stevens Process......Page 6797
4.3.2.2 Aprotic Bamford-Stevens Process......Page 6798
4.3.3 Shapiro Reaction......Page 6800
4.3.4 Neber Rearrangement......Page 6807
4.3.5 Amadori Rearrangement......Page 6810
4.3.6 References......Page 6812
4.4.1.1 General Aspects......Page 6815
4.4.1.2 Mechanism and Stereoselectivity......Page 6818
4.4.2.1 Under Basic Conditions......Page 6820
4.4.2.2 Under Acidic Conditions......Page 6822
4.4.3.1 Via Hydrazides......Page 6826
4.4.3.2 Via Acyl Chlorides......Page 6827
4.43.3 Via Mixed Anhydrides......Page 6830
4.4.3.4 By Use of Diphenyl Phosphorazidate......Page 6831
4.4.4.1 With Carboxylic Acids......Page 6837
4.4.4.2 With Ketones......Page 6840
4.4.5.1 Under Basic Conditions......Page 6841
4.4.5.2 Under Neutral Conditions......Page 6844
4.4.6 References......Page 6845
4.5.1 Introduction......Page 6849
4.5.1.1 Intermolecular Reactions with Allylic Rearrangement......Page 6850
4.5.1.2 Intramolecular Allylic Rearrangements......Page 6853
4.5.2.1 Oxygen-Halogen Transpositions......Page 6854
4.5.2.2 Oxygen-Oxygen Transpositions......Page 6855
4.5.2.3 Oxygen-Sulfur Transpositions......Page 6857
4.5.2.4 Oxygen-Nitrogen Transpositions......Page 6862
4.5.2.5 Oxygen-Phosphorus Transpositions......Page 6864
4.5.2.7 Sulfur-Nitrogen Transpositions......Page 6866
4.5.3.1 C-C Bond Formation by Nucleophilic Attack on the Allylic System......Page 6867
59299_v06_04_05b.pdf......Page 6874
4.5.3.2 C-C Bond Formation with the Allyl System as the Nucleophile......Page 6882
4.5.4 1,3-Heteroatom-Hydrogen Transpositions......Page 6885
4.5.5 1,3-Hydrogen-Hydrogen Transpositions: Isomerization of Allyl and Propargyl Systems......Page 6886
4.5.6 References......Page 6887
4.6.1 Introduction......Page 6892
4.6.2.1 Rearrangement of Ethers......Page 6893
4.6.2.2 Rearrangement of Sulfides and Amines......Page 6911
4.6.3.1 Sulfoxide-Sulfenate Rearrangement......Page 6918
4.6.3.2 Selenoxide-Selenate Rearrangement......Page 6923
4.6.3.3 Introduction of Allylic Nitrogen......Page 6924
4.6.4 References......Page 6925
4.7 Polonovski- and Pummerer-Type Reactions and the Nef Reaction......Page 6928
4.7.1 Introduction......Page 6929
4.7.2.1 Mechanism......Page 6930
4.7.2.2 Carbon-Hydrogen Elimination Reactions......Page 6931
4.7.2.3 Carbon-Carbon Fragmentation Reactions......Page 6938
4.7.2.4 Other Reactions......Page 6941
4.7.2.6 Silicon and Selenium Polonovski Reactions......Page 6942
4.7.3.1 Mechanism, Regio- and Stereo-Chemistry......Page 6943
4.7.3.2 Preparation and Elaboration of alpha-Acyloxy Sulfides......Page 6945
4.7.3.3 Inter- and Intra-Molecular Reactions of alpha-Acyloxy Sulfides or Their Thionium Ion Precursors with Nucleophiles......Page 6946
4.7.3.4 Reactions of alpha-Acyl Sulfides with pi-Systems......Page 6948
4.7.3.5 Vinyl Sulfides......Page 6950
4.7.3.6 Additive and Vinylogous Additive Pummerer Reactions......Page 6951
59299_v06_04_07b.pdf......Page 6952
4.7.3.7 Sila-Pummerer Reactions: Preparation of Trimethylsiloxy Sulfides......Page 6953
4.7.3.9 Other Activating Reagents......Page 6955
4.7.4.1 Mechanism......Page 6956
4.7.4.2 Scope and Limitations......Page 6958
4.7.5 References......Page 6963
5.1 Eliminations to Form Alkenes, Allenes and Alkynes and Related Reactions......Page 6967
5.1.2.1 The E1 Mechanism (Elimination, Monomolecular)......Page 6968
5.1.2.2 The E1cB Mechanism (Elimination, Monomolecular, Conjugate Base)......Page 6969
5.1.2.3 The E2 Mechanism (Elimination, Bimolecular)......Page 6970
5.1.2.4 Stereoselectivity......Page 6971
5.1.2.5 Orientation......Page 6973
5.1.2.6 E1 versus E2 versus E1cB......Page 6974
5.1.2.7 The Elimination/Substitution Ratio......Page 6975
5.1.3.1 Dehydrohalogenation of Alkyl Halides......Page 6976
5.1.3.3 Dehydration of Alcohols......Page 6977
5.1.3.5 Alkenes from Quaternary Ammonium Salts......Page 6978
5.1.3.6 Alkenes from p-Toluenesulfonylhydrazones......Page 6979
5.1.4.1 Dehydrohalogenation of 1,2- or 1,1-Dihaloalkanes......Page 6980
5.1.4.2 Elimination of 'Acids' Other Than Hydrogen Halides......Page 6984
5.1.4.3 Dehalogenation of 1,1- or 1,2-Dihaloalkenes and Other Eliminations of Two Vicinal Leaving Groups......Page 6985
5.1.4.4 Oxidative Decomposition of 1,2-Dihydrazones and 1-Amino-1,2,3-Triazoles......Page 6986
5.1.5.1 Dehydrohalogenation of Vinylic or Allylic Halides......Page 6987
5.1.5.4 Dehalogenation of gem-Dibromocyclopropanes......Page 6988
5.1.6 References......Page 6989
5.2.1 Introduction......Page 6992
5.2.2.1 1,2- and 1,4-Dihalides......Page 6993
5.2.2.2 Halohydrins......Page 6994
5.2.3 Reductive Elimination of Oxiranes and Thiiranes......Page 6997
5.2.4.1 Fragmentation of Thioxocarbonates......Page 6999
5.2.4.2 Fragmentation of 2-Methoxy-, 2-Acetoxy- and 2-Dimethylamino-1,3-Dioxolanes......Page 7001
5.2.4.4 Transition Metal Mediated Deoxygenation of vic-Diols......Page 7002
5.2.4.5 Reductive Elimination of Acyclic vic-Diester Derivatives......Page 7003
5.2.5.1 The Julia Alkenation......Page 7004
5.2.6 Vicinal Desilylation......Page 7017
5.2.6.1 beta-Silyl Sulfones......Page 7019
5.2.6.2 beta-Silylhaloalkanes......Page 7021
5.2.6.3 beta-Silyl Esters and Ethers......Page 7022
5.2.7 References......Page 7024
5.3.1 Introduction......Page 7028
5.3.2.1 Introduction......Page 7029
5.3.2.2 Stereo- and Regio-Chemistry......Page 7030
5.3.3.1 Introduction......Page 7033
5.3.3.2 Stereo- and Regio-Chemistry......Page 7035
5.3.3.3 Applications of Sulfoxide Elimination in Synthesis......Page 7037
5.3.4.1 Introduction: Stereo- and Regiochemistry......Page 7043
5.3.4.2 Applications of Selenoxide Elimination......Page 7045
5.3.5.1 Introduction......Page 7050
5.3.5.2 Applications in Synthesis......Page 7052
5.3.7 References......Page 7053
5.4.1.1 Definition......Page 7057
5.4.1.2 History......Page 7058
5.4.1.3 Mechanism and Stereochemistry......Page 7059
5.4.2.1 Open Chains and Normal Rings......Page 7060
5.4.2.2 Medium-Sized and Large Rings......Page 7066
5.4.2.3 Alkynones (Eschenmoser-Type)......Page 7074
5.4.2.4 Silicon- and Metal-Assisted Fragmentations......Page 7077
5.4.3 Beckmann Fragmentation......Page 7082
5.4.4 Miscellaneous......Page 7083
5.4.5 References......Page 7085
A......Page 7087
B......Page 7089
C......Page 7094
D......Page 7098
E......Page 7101
F......Page 7102
G......Page 7105
H......Page 7108
I......Page 7112
J......Page 7114
K......Page 7115
L......Page 7121
M......Page 7124
N......Page 7130
O......Page 7133
P......Page 7134
R......Page 7138
59299_v06_aindxc.pdf......Page 7140
S......Page 7141
T......Page 7149
V......Page 7153
W......Page 7155
Y......Page 7158
Z......Page 7159
A......Page 7161
B......Page 7169
C......Page 7171
D......Page 7176
E......Page 7178
F......Page 7181
G......Page 7182
H......Page 7183
I......Page 7185
K......Page 7187
L......Page 7188
M......Page 7189
N......Page 7191
O......Page 7192
P......Page 7194
Q......Page 7200
S......Page 7201
T......Page 7205
V......Page 7209
Z......Page 7210
Front Matter......Page 7211
Table of Contents......Page 7213
Preface......Page 7216
Contributors to Volume 7......Page 7218
Abbreviations......Page 7221
1.1.1 Introduction......Page 7224
1.1.4 Formation of R-M Bonds (M = Group I and II Metal)......Page 7225
1.1.6 Formation of R-M Bonds (M = Transition Metal)......Page 7226
1.1.7 Formation of R-C Bonds......Page 7227
1.1.7.2 Alkane Dehydrodimerization......Page 7228
1.1.7.4 Dehydrogenation and Aromatization......Page 7229
1.1.7.6 Other Reactions......Page 7230
1.1.9 Formation of R-N Bonds......Page 7231
1.1.11.1 Autoxidation......Page 7233
1.1.11.2 Hydroxylation and Related Reactions......Page 7234
1.1.12 Formation of R-X Bonds (X = S, Se, Te)......Page 7237
1.1.14 Formation of R-X Bonds (X = C1, Br, I)......Page 7238
1.1.15 References......Page 7240
1.2.1 Introduction......Page 7244
1.2.2.2 Reactivity......Page 7245
1.2.3.1 Intermolecular......Page 7246
1.2.3.2 Intramolecular......Page 7250
1.2.4 Intramolecular Insertion into sp^2 C-H Bonds......Page 7254
1.2.5 References......Page 7260
1.3.1.1 Topics Covered......Page 7262
1.3.2 Intramolecular Functionalizations in the Vicinity of Existing Substrate Functional Groups......Page 7263
1.3.3.1 Remote Photochemical Functionalization......Page 7265
1.3.3.3 Directed Chlorinations......Page 7266
1.3.4 Selective Reactions in Molecular Complexes......Page 7272
1.3.5 Future Prospects for Remote Oxidations......Page 7273
1.3.6 References......Page 7274
1.4.1 Introduction......Page 7276
1.4.2.3 Use of Microorganisms......Page 7278
1.4.3.1 Acyclic Hydracarbons and Their Functionalized Derivatives......Page 7279
1.4.3.2 Cyclic Hydrocorbons and Their Functionalized Derivatives......Page 7281
1.4.3.3 Isoprenoids......Page 7285
1.4.3.4 Alkaloids......Page 7288
1.4.4 Microbial Oxidation of Steroids......Page 7289
1.4.4.1 Dehydrogenation......Page 7290
1.4.4.2 Hydroxylation......Page 7291
1.4.5 Special Methods......Page 7297
1.4.5.1 Benzylic Substrates......Page 7298
1.4.5.2 Allylic Substrates......Page 7300
1.4.5.3 Nuclear Hydroxylation of Aromatic Hydrocarbons......Page 7301
1.4.6.1 Oxidations with Isolated Enzymes......Page 7302
1.4.7 References......Page 7303
2.1.1 Introduction......Page 7306
2.1.2.1 Selenium Dioxide Based Reagents......Page 7307
2.1.2.2 Metal Acetates and Related Reagents......Page 7315
2.1.2.3 Miscellaneous Reagents......Page 7318
2.1.3.1 Chromium(VI)-Based Reagents......Page 7322
2.1.3.2 Other Transition Metal Catalyzed Allylic Oxidations......Page 7330
2.1.3.3 Selenium-Based Reagents......Page 7331
2.1.3.4 Singlet Oxygen......Page 7333
2.1.3.5 Miscellaneous Reagents......Page 7335
2.1.4 References......Page 7336
2.2.1 Introduction......Page 7341
2.2.2.1 Halogenation......Page 7342
2.2.2.2 Dehydrohalogenation......Page 7344
2.2.3 Sulfur-Based Reagents......Page 7346
2.2.3.1 Sulfur(II) Reagents......Page 7347
2.2.3.2 Sulfur(IV) Reagents......Page 7349
2.2.4 Selenium-Based Reagents......Page 7350
2.2.4.1 Selenium(II) Reagents......Page 7351
2.2.4.2 Selenium(IV) Reagents......Page 7354
2.2.5 Dichlorodicyanoquinone and Related Reagents......Page 7357
2.2.6 Noble Metals and Their Salts......Page 7361
2.2.7 Miscellaneous Chemical Methods......Page 7364
2.2.8 Microbial and Enzymatic Methods......Page 7367
2.3.10 References......Page 7368
2.3.1 Introduction......Page 7372
2.3.2.1 Saturated Ketones......Page 7373
2.3.2.2 alpha,beta-Unsaturated Ketones: sp^3 Center......Page 7395
59299_v07_02_03b.pdf......Page 7397
2.3.2.4 Esters and Lactones......Page 7400
2.3.2.5 Amides and Lactams......Page 7404
2.3.2.6 Carboxylic Acids......Page 7406
2.3.3.1 Oxime Acetates and Nitrones......Page 7407
2.3.4 References......Page 7408
2.4.1 Introduction......Page 7413
2.4.2 The Pummerer Rearrangement......Page 7414
2.4.3.1 Reaction with Carboxylic Anhydrides......Page 7416
2.4.3.2 Pummerer Rearrangement with alpha-Alkylation and Arylation......Page 7419
2.4.3.3 Pummerer Rearrangement with Participation by Nitrogen......Page 7421
2.4.3.4 Pummerer Rearrangement in Hydroxylic Solvents......Page 7422
2.4.3.5 Miscellaneous and Abnormal Pummerer Rearrangements......Page 7423
2.4.4 alpha-Halogenation of Sulfides......Page 7426
2.4.4.1 Miscellaneous Routes to alpha-Chloro Sulfides......Page 7432
2.4.5 References......Page 7434
2.5 Oxidation Adjacent to Nitrogen......Page 7437
2.5.2.1 The Nef Reaction......Page 7438
2.5.2.2 The Meyer Reaction......Page 7440
2.5.3.2 Chromium and Manganese Reagents......Page 7441
2.5.3.5 Amine Oxides......Page 7442
2.5.3.6 Miscellaneous Oxidation Reactions of Tertiary Amines......Page 7443
2.5.4.2 N-Nitrosamines......Page 7444
2.5.4.3 Amides......Page 7445
2.5.4.4 Urethanes......Page 7446
2.5.4.5 Miscellaneous Methods......Page 7447
2.5.5.1 Conversion into Aldehydes and Ketones......Page 7448
2.5.6.1 Alkylation......Page 7449
2.5.7.1 Lactams/Amides......Page 7450
2.5.7.4 Hydrazones/Oximes......Page 7451
2.5.8 References......Page 7452
2.6.1 Introduction......Page 7455
2.6.2.1 Introduction......Page 7456
2.6.2.2 Reaction Conditions......Page 7457
2.6.2.3 Selectivity of Reaction and Application in Synthesis......Page 7458
2.6.3.1 Introduction......Page 7464
2.6.3.3 Selectivity of Reaction and Application in Synthesis......Page 7465
2.6.4.3 Electrochemical Oxidation......Page 7467
2.6.5 References......Page 7468
2.7 Oxidation Adjacent to Oxygen of Alcohols by Chromium Reagents......Page 7471
2.7.2.3 In DMF/DMSO with Catalytic Sulfuric Acid......Page 7472
2.7.2.5 In Aqueous Sulfuric Acid/Acetone (Jones Oxidation)......Page 7473
2.7.3.1 Chromium(VI) Oxide(Pyridine)_2......Page 7476
2.7.3.3 Pyridinium Chlorochromate (PCC)......Page 7480
2.7.3.4 Other Chromates......Page 7487
2.7.3.5 Pyridinium Dichromate (PDC)......Page 7492
2.7.3.6 Other Dichromates......Page 7497
2.7.4.3 Catalytic Chromium(VI) Oxide Oxidations......Page 7498
2.7.5.1 On Inert Inorganic Supports......Page 7499
2.7.5.2 On Resins/Polymers......Page 7500
2.7.5.3 On Carbon......Page 7502
2.7.6.2 Trimethylsilyl Chlorochromate (TMSCC)......Page 7503
2.7.6.3 Alkyl Metal Chromates......Page 7505
2.7.7 References......Page 7506
2.8.1 Introduction......Page 7510
2.8.2 General Mechanism of Activated DMSO Oxidation......Page 7511
2.8.3.1 DMSO - Dicyclohexylcarbodiimide......Page 7512
2.8.3.2 DMSO - Acetic Anhydride......Page 7513
2.8.3.3 DMSO - Trifluoroacetic Anhydride......Page 7514
2.8.3.5 DMSO-Oxalyl Chloride......Page 7515
2.8.3.7 DMSO - Chlorine and Halogen Derivatives......Page 7517
2.8.4 Oxidation of Alcohols......Page 7518
2.8.5 Conclusions......Page 7521
2.8.6 References......Page 7522
2.9.2.1 Selective Preparation of Aldehydes......Page 7523
2.9.2.2 Selective Preparation of Lactones from Diols......Page 7530
2.9.3.1 Selective Preparation of Ketones......Page 7536
2.9.4 Conclusion......Page 7542
2.9.5 References......Page 7543
2.10.1 Introduction......Page 7546
2.10.2.1 Imidazolones......Page 7547
2.10.2.4 Estrogens......Page 7548
2.10.2.5 Miscellaneous......Page 7550
2.10.3.1 Indoles......Page 7552
2.10.3.3 Dihydrocoumarins......Page 7553
2.10.4.3 Quinol Acetates......Page 7555
2.10.5 Nonmetallated Intermediates......Page 7556
2.10.5.1 Hydroquinones......Page 7557
2.10.5.3 Anthracycline Relatives......Page 7558
2.10.6 References......Page 7559
2.11.1 Introduction......Page 7561
2.11.2.1 Towards Rubradirin......Page 7562
2.11.2.4 Lavendamycin Pharmacophores......Page 7563
2.11.2.5 Methoxatin......Page 7565
2.11.3.3 Saframycin B......Page 7566
2.11.3.4 Demethoxydaunomycinone......Page 7567
2.11.4.1 Demethoxydaunomycinone......Page 7568
2.11.4.2 Towards Mitomycin C......Page 7569
2.11.5.1 Metacyclophanes......Page 7570
2.11.5.3 Miscellaneous......Page 7571
2.11.6 References......Page 7572
3.1 Addition Reactions with Formation of Carbon-Oxygen Bonds: (i) General Methods of Epoxidation......Page 7573
3.1.2.1 General Survey of Reactivity......Page 7574
3.1.2.2 Epoxidations with m-Chloroperbenzoic Acid (MCPBA)......Page 7575
3.1.2.3 Some of the Commonly Used Peroxy Acids and Related Reagents......Page 7588
3.1.3.1 Epoxidations of Alkenes Lacking Directing Groups......Page 7591
3.1.3.2 Epoxidations of Cyclic Alkenes Having Directing Groups......Page 7592
3.1.3.3 Epoxidations of Acyclic Alkenes Having Directing Groups......Page 7594
3.1.5 Epoxidations with Hydrogen Peroxide......Page 7597
3.1.7 Epoxidations via Catalysis by First-Row Transition Metal Complexes......Page 7598
3.1.9 Chemoselective Epoxidations......Page 7600
3.1.10 References......Page 7602
3.2 Addition Reactions with Formation of Carbon-Oxygen Bonds: (ii) Asymmetric Methods of Epoxidation......Page 7604
3.2.2 Fundamental Elements of Titanium Tartrate Catalyzed Asymmetric Epoxidation......Page 7605
3.2.3.1 Stoichiometry......Page 7608
3.2.3.4 Oxidant and Epoxidation Solvent......Page 7609
3.2.3.6 Titanium Alkoxides......Page 7610
3.2.4 Sources of Allylic Alcohols......Page 7611
3.2.5.1 Allyl Alcohol......Page 7612
3.2.5.2 2-Substituted Allyl Alcohols......Page 7613
3.3.5.3 (3E)-Substituted Allyl Alcohols......Page 7615
3.2.5.4 (3Z)-Monosubstituted Allyl Alcohols......Page 7620
3.2.5.5 (2,3E)-Disubstituted Allyl Alcohols......Page 7621
3.2.5.6 (2,3Z)-Disubstituted Allyl Alcohols......Page 7623
3.2.5.8 2,3,3-Trisubstituted Allyl Alcohols......Page 7624
3.2.5.9 1-Substituted Allyl Alcohols: Kinetic Resolution......Page 7626
59299_v07_03_02b.pdf......Page 7630
3.2.5.10 1,1-Disubstituted Allyl Alcohols......Page 7632
3.2.5.11 Homoallylic, Bis(Homoallylic) and Tris(Homoallylic) Alcohols......Page 7634
3.2.6 Mechanism of the Titanium Tartrate Catalyzed Asymmetric Epoxidation......Page 7635
3.2.7.1 Ti_2 (Tartrate)_2 Complex......Page 7637
3.2.7.2 Ti_2 (Tartrate) Complex......Page 7638
3.2.7.4 [Ti(OPr^i )_2 Cl_2 (Tartrate)] Complexes......Page 7639
3.2.8 Other Asymmetric Epoxidation Methods......Page 7640
3.2.9 Homochiral Epoxides via Asymmetric Dihydroxylation......Page 7644
3.2.10 References......Page 7647
3.3.1 Introduction......Page 7652
3.3.2.1 Osmium Tetroxide......Page 7654
3.3.2.3 Methods Involving Halohydrin Esters as Intermediates......Page 7659
3.3.3.2 Hydrogen Peroxide with an Oxide Catalyst......Page 7661
3.3.4 References......Page 7662
3.4.1 Introduction......Page 7664
3.4.2.2 Solvents......Page 7665
3.4.2.3 Reoxidants......Page 7666
3.4.3.1 Oxidation of Terminal Alkenes Bearing Various Functional Groups......Page 7667
3.4.3.2 Synthetic Applications......Page 7669
3.4.4.2 Regioselective Oxidation of alpha,beta- and beta,gamma-Unsaturated Carbonyl Compounds......Page 7677
3.4.4.3 Regioselective Oxidation of Allyl and Homoallyl Ethers and Esters......Page 7680
3.4.5 References......Page 7682
3.5 Addition Reactions with Formation of Carbon-Nitrogen Bonds......Page 7684
3.5.2.1 Aziridines with Nitrogen Unsubstituted......Page 7685
3.5.2.2 N-Alkyl- and N- Alkenyl-Aziridines......Page 7689
3.5.2.3 N-Aryl- and N-Heteroaryl-Aziridines......Page 7691
3.5.2.4 N-Acyl- and N-Cyano-Aziridines and Related Compounds......Page 7692
3.5.2.5 N- Amiwaziridines, N-Phosphonylaziridines......Page 7695
3.5.2.6 Aziridines N-Substituted with O or S......Page 7698
3.5.3.1 Formation of Diamines......Page 7699
3.5.3.2 Formation of Diazides......Page 7702
3.5.4.1 Oxyamination and Oxyamidation......Page 7703
3.5.5.1 Addition of Nitrogen and Sulfur......Page 7708
3.5.5.2 Addition of Nitrogen and Selenium......Page 7710
3.5.5.3 Addition of Nitrogen and Tellurium......Page 7712
3.5.6.2 Addition of Nitrogen and Chlorine......Page 7713
3.5.6.3 Addition of Nitrogen and Bromine......Page 7715
3.5.6.4 Addition of Nitrogen and Iodine......Page 7716
3.5.6.5 Iodolactamizations and Related Reactions......Page 7718
3.5.7.1 Addition to Dienes......Page 7719
3.5.10 Additions Cleaving the C=C Bond......Page 7721
3.5.11 References......Page 7723
3.6.2.1 Formation of Thiiranes......Page 7729
3.6.2.2 Electrophilic Sulfur Additions......Page 7730
3.6.2.3 Radical Sulfur Additions......Page 7732
3.6.3.1 Regiochemistry of Additions......Page 7734
3.6.3.2 Seleno-Heteroatom Additions......Page 7736
3.6.3.3 Selenium-Induced Cyclizations......Page 7737
3.6.4 References......Page 7739
3.7.1 Oxidative Halogenation with Halometallic Reagents......Page 7741
3.7.2 Halofunctionalizations with Hg^II , TI^III and Te^IV Reagents......Page 7747
3.7.3 Oxidative Halogenation with Nonmetallic Reagents......Page 7749
3.7.4 Miscellaneous (Photochemical and Enzymatic Reactions)......Page 7752
3.7.5 References......Page 7753
3.8.1 Introduction......Page 7755
3.8.2.1 Ozone......Page 7757
3.8.3.1 Ozone......Page 7758
3.8.3.2 Permanganate......Page 7772
3.8.3.4 Ruthenium Tetroxide......Page 7778
3.8.3.5 Hexavalent Chromium Compounds......Page 7785
3.8.4.1 Ozone Followed by an Oxidative Work-up......Page 7788
3.8.4.2 Permanganate Reactions......Page 7792
3.8.4.5 t-Butyl Peroxide and Molybdenum Dioxide Diacetylacetonate......Page 7801
3.8.5.2 Ethanethiol and Aluminum Chloride......Page 7802
3.8.6 References......Page 7803
4.1.1 Introduction......Page 7806
4.1.2 Oxidation with Alkaline Hydrogen Peroxide......Page 7808
4.1.4 Oxidation with Trimethylamine N-Oxide......Page 7810
4.1.5 Autoxidation......Page 7811
4.1.6 Oxidation by Peracids......Page 7812
4.1.7.1 Chromic Acid......Page 7813
4.1.7.3 Pyridinium Chlorochromate......Page 7814
4.1.9 Electrochemical Oxidation......Page 7815
4.1.10 Oxidation by Carbonyl Compounds to Produce Alkenes......Page 7816
4.1.12 Brominolysis of C-B Bonds......Page 7817
4.1.14.1 Synthesis of Primary Amines......Page 7819
4.1.15 Replacement of Boron by Sulfur or Selenium......Page 7820
4.1.16 References......Page 7821
4.2.1 Introduction......Page 7825
4.2.2.2 Unactivated Carbon-Tin Bonds......Page 7826
4.2.2.3 Allylic Stannanes......Page 7828
4.2.2.4 Vinylstannanes......Page 7832
4.2.2.5 gamma-Trialkylstannyl Alcohols; Oxidative 1,4-Fragmentation......Page 7833
4.2.2.6 beta-Stannyl Hydrazones, Oximes and Carboxylic Acids......Page 7840
4.2.3.1 pi- Allylpalladium Complexes......Page 7841
4.2.3.2 Cyclopalladation-Oxidation......Page 7842
4.2.4.1 Introduction......Page 7843
4.2.4.2 Oxymercuration-Oxidative Demercuration......Page 7844
4.2.4.3 Miscellaneous Oxidations......Page 7849
4.2.5 References......Page 7850
4.3.1 Introduction......Page 7852
4.3.2.1 By Hydrosilylation......Page 7853
4.3.2.2 From Functionalized Silanes......Page 7857
4.3.3 Miscellaneous......Page 7860
4.3.4 References......Page 7861
4.4.2.1 Oxidation with Dimethyl Sulfoxide......Page 7863
4.4.3 The Kröhnke Oxidation......Page 7867
4.4.4 The Hass-Bender Reaction......Page 7869
4.4.5.1 Pyridine N-Oxides and Derivatives......Page 7871
4.4.5.2 N-Hydroxypyridones......Page 7872
4.4.6 Chromium-Based Methods......Page 7873
4.4.7.1 Silver Nitrate......Page 7874
4.4.7.2 Other Metal Nitrates and Nitrites......Page 7875
4.4.8 The Sommelet Oxidation......Page 7876
4.4.9.1 Oxidation via the Pummerer Rearrangement......Page 7877
4.4.9.2 Triflamides and Triflic Hydrazides......Page 7878
4.4.10 References......Page 7879
5.1.2.1 General......Page 7881
5.1.2.2 Stereochemistry......Page 7882
5.1.3.3 Regiochemistry......Page 7883
5.1.3 Reaction Methods......Page 7884
5.1.4.2 Competitive Baeyer-Villiger Reactions......Page 7885
5.1.5.1 Acyclic Aliphatic Ketones......Page 7886
5.1.5.3 Monocyclic and Spirocyclic Ketones......Page 7888
5.1.5.4 Fused Ring Bicyclic and Polycyclic Ketones......Page 7890
5.1.5.5 Bridged Bicyclic and Polycyclic Ketones......Page 7892
5.1.5.8 Aryl- and Alkyl-Carbaldehydes......Page 7894
5.1.6 Side Reactions......Page 7895
5.1.7 References......Page 7897
5.2.1 Introduction......Page 7899
5.2.2.1 Mechanism and Stereochemistry......Page 7900
5.2.2.2 Ketoximes......Page 7901
5.2.3 Addition Reactions......Page 7905
5.2.3.1 Intermolecular Reactions......Page 7906
5.2.3.2 Intramolecular Reactions......Page 7907
5.2.4.1 Carbon-Assisted Fragmentations......Page 7908
5.2.4.2 Heteroatom-Assisted Fragmentations......Page 7910
5.2.5 References......Page 7911
5.3.2 Sodium Bismuthate......Page 7913
5.3.3 Pentavalent Organobismuth Reagents......Page 7914
5.3.4 Cerium(IV) Reagents......Page 7915
5.3.8 Iodo Reagents......Page 7916
5.3.10 Anodic Oxidation......Page 7917
5.3.13.1 General Characteristics......Page 7918
5.3.13.3 Applications in Organic Synthesis......Page 7919
5.3.14 References......Page 7925
5.4.1 Introduction......Page 7927
5.4.2.2 Lead(IV) Carboxylates......Page 7928
5.4.2.3 O-Acyl Oximes and O-Acyl Thiohydroxamates......Page 7929
5.4.3.4 O-Acyl Benzophenone Oximes and t-Butyl Thiol......Page 7930
5.4.3.6 Decarbonylation Methods......Page 7931
5.4.4.2 1,4-Dicarboxylic Acids......Page 7932
5.4.5.1 Acyl Hypohalites and Related Species......Page 7933
5.4.5.3 O-Acyl Thiohydroxamates and Halogen Donor Solvents......Page 7934
5.4.6 Decarboxylative Chalcogenation and Phosphorylation......Page 7935
5.4.6.2 Selenation and Telluration......Page 7936
5.4.7 Decarboxylative Oxygenation......Page 7937
5.4.9 Decarboxylation with Subsequent C-C Bond Formation......Page 7939
5.4.9.1 Addition to C-C Multiple Bonds......Page 7940
5.4.9.2 Addition to C-Heteroatom Multiple Bonds......Page 7941
5.4.9.3 Addition to Aromatic Systems......Page 7942
5.4.10 References......Page 7943
6.1.1 Introduction......Page 7945
6.1.2.1 Primary Amines......Page 7946
6.1.2.2 Hydrazones, Hydrazines and Hydroxylamines......Page 7952
6.1.3.1 Secondary Amines......Page 7955
6.1.3.2 Hydrazines and Hydroxylamines......Page 7957
6.1.4.1 Formation of N-Oxides......Page 7958
6.1.5.1 N-Oxidation of Heteroaromatic Amines......Page 7959
6.1.5.3 Oxidation of Azo to Azoxy Compounds......Page 7960
6.1.5.4 Oxidation of Oximes and Nitroso Compounds......Page 7961
6.1.6 Oxidation of Phosphorus......Page 7962
6.1.7 References......Page 7963
6.2 Oxidation of Sulfur, Selenium and Tellurium......Page 7967
6.2.2.1 Oxidation of Thiols to Disulfides by Molecular Oxygen and Chemical Reagents......Page 7968
6.2.2.2 Oxidation of Sulfides to Sulfoxides by Chemical Reagents......Page 7972
6.2.2.3 Oxidation of Sulfoxides to Sulfones by Chemical Reagents......Page 7976
6.2.3.1 Oxidation of Selenols to Diselenides and Further Oxidized Species by Chemical Reagents......Page 7979
6.2.3.2 Oxidation of Selenides to Selenoxides by Chemical Reagents......Page 7980
6.2.3.3 Oxidation of Selenides and Selenoxides to Selenones......Page 7983
6.2.4.1 Oxidation of Tellurols to Ditellurides and Further Oxidized Species by Chemical Reagents......Page 7984
6.2.4.2 Oxidation of Tellurides to Telluroxides......Page 7985
6.2.4.3 Oxidation of Tellurides to Tellurones......Page 7986
6.2.5.1 Synthesis of Optically Active Sulfoxides by Chemical Oxidation......Page 7987
6.2.5.2 Synthesis of Optically Active Sulfoxides by Biological Oxidation......Page 7988
6.2.5.3 Synthesis of Optically Active Selenoxides by Chemical Oxidation......Page 7989
6.2.6 References......Page 7990
7.1 Oxidation by Electrochemical Methods......Page 7998
7.1.1.2 Interface Reactions......Page 7999
7.1.2.1 Apparatus......Page 8000
7.1.2.2 Techniques......Page 8001
7.1.3.1 Oxidation of Carbon-Hydrogen and Carbon-Carbon Single Bonds......Page 8002
7.1.3.2 Oxidation of Unsaturated Systems......Page 8003
7.1.3.3 Oxidation of Systems Bearing Lone Pairs of Electrons......Page 8011
7.1.3.4 Oxidation of Anions......Page 8014
7.1.4.1 Oxidation Using Mediators......Page 8016
7.1.4.2 Formation of Active Species......Page 8019
7.1.5 References......Page 8020
7.2.1 Introduction......Page 8023
7.2.2.1 Alkenes and Enols......Page 8024
7.2.2.2 Allylic Alcohols......Page 8029
7.2.2.3 Cyclopropanes and Cyclobutanes......Page 8032
7.2.2.4 Miscellaneous Functional Group Rearrangements......Page 8034
7.2.3 Oxidative Skeletal Rearrangement......Page 8035
7.2.3.1 Alkenes and Enols......Page 8036
7.2.3.2 Dienes......Page 8040
7.2.3.4 Cyclopropanes and Cyclobutanes......Page 8041
7.2.3.5 Miscellaneous Skeletal Rearrangements......Page 8043
7.2.4 References......Page 8044
7.3.1 Introduction......Page 8046
7.3.2.4 Potassium Dichromate and Epoxidizing Agents......Page 8048
7.3.3.2 Sodium Methoxide......Page 8049
7.3.3.6 Periodates......Page 8050
7.3.3.8 Chromium(VI)......Page 8051
7.3.4.2 Thallium Trinitrate......Page 8052
7.3.5 Conclusions......Page 8053
7.3.6 References......Page 8054
7.4 Electron-Transfer Oxidation......Page 8056
7.4.1 Scope and Definitions......Page 8057
7.4.2.1 Oxidation Potentials of Organic Compounds......Page 8059
7.4.3 Generic Behavior of Radical Ions as Reactive Intermediates in Electron-Transfer Oxidation......Page 8061
7.4.3.1 Chemistry of Organic Radical Cations......Page 8064
7.4.3.2 The Follow-up Reactions of Organic Radical Cations......Page 8067
7.4.3.3 Chemistry of Organic Radical Anions......Page 8068
7.4.4 Thermal and Photochemical Activation of Electron-Transfer Oxidation......Page 8069
7.4.4.1 Thermal Osmylation of Naphthalene, Anthracene and Phenanthrene......Page 8070
7.4.4.3 Time-Resolved Spectra of Arene Radical Cations in Charge-Transfer Osmylation......Page 8071
7.4.4.4 Common Features in Thermal and Charge-Transfer Osmylations......Page 8072
7.4.4.5 Electron Transfer in the Charge-Transfer Osmylation of Arenes......Page 8073
7.4.4.6 Electron Transfer as the Common Theme in Arene Osmylation......Page 8074
7.4.5.1 EDA Complexes as Intermediates in Mercuration and Thallation. Comparison of Their Ground and CT Excited States......Page 8075
7.4.5.2 Comparison of the Activation Barriers for Mercuration and Thallation......Page 8076
7.4.5.4 The Relevance of Arene Radical Cations in Electrophilic Aromatic Substitution......Page 8077
7.4.5.5 Electron Transfer versus Electrophilic Pathways for Aromatic Substitution......Page 8079
7.4.6.1 Donor Radical Cations......Page 8080
7.4.6.2 Acceptor Radical Anions......Page 8089
7.4.7 References......Page 8092
A......Page 8097
B......Page 8099
C......Page 8104
D......Page 8108
E......Page 8111
F......Page 8112
G......Page 8114
H......Page 8117
I......Page 8121
J......Page 8122
K......Page 8123
L......Page 8128
M......Page 8131
N......Page 8137
O......Page 8139
P......Page 8141
R......Page 8143
59299_v07_aindxc.pdf......Page 8145
S......Page 8146
T......Page 8154
V......Page 8157
W......Page 8158
Y......Page 8161
Z......Page 8163
A......Page 8164
B......Page 8171
C......Page 8175
D......Page 8182
E......Page 8185
F......Page 8187
H......Page 8188
I......Page 8191
K......Page 8192
M......Page 8194
59299_v07_sindxb.pdf......Page 8195
N......Page 8196
O......Page 8198
P......Page 8201
R......Page 8207
S......Page 8208
T......Page 8213
V......Page 8216
Z......Page 8217
Front Matter......Page 8218
Table of Contents......Page 8220
Preface......Page 8223
Contributors to Volume 8......Page 8225
Abbreviations......Page 8228
1.1.1 Introduction......Page 8231
1.1.1.1 Kinetics and Mechanism......Page 8232
1.1.2.1 Acyclic Carbonyl Compounds......Page 8233
1.1.2.2 Cyclic Carbonyl Compounds......Page 8235
1.1.3.1 Acyclic Carbonyl Compounds......Page 8237
1.1.3.2 Cyclic Carbonyl Compounds......Page 8244
1.1.4.1 Reduction of Enones......Page 8245
1.1.4.2 Aldehydes versus Ketones......Page 8246
1.1.4.3 Ketones versus Other Carbonyl Groups......Page 8248
1.1.4.5 alpha-Halo Ketones......Page 8249
1.1.5.1 Silicon......Page 8250
1.1.5.2 Tin......Page 8251
1.1.6 References......Page 8252
1.2.1 Introduction......Page 8255
1.2.2.1 General Considerations and Comparisons to Carbonyl Reductions......Page 8256
1.2.2.2 Reduction of Preformed Imines and Iminium Salts of Ammonia, Primary and Secondary Amines......Page 8257
1.2.2.3 Reduction of In Situ Generated Imines and Iminium Salts of Ammonia, Primary and Secondary Amines; Reductive Amination......Page 8277
1.2.2.4 Reduction of Enamines via Iminium Ion Intermediates......Page 8285
1.2.3.1 Reduction of Oximes, Oxime Ethers and Oxime Esters to Hydroxylamines and Derivatives......Page 8290
1.2.3.3 Stereoselectivity of Reductions of Cyclic Oximes and Oxime Derivatives......Page 8294
1.2.3.4 Reduction of Hydrazone Derivatives to Hydrazine Derivatives......Page 8300
1.2.4 References......Page 8304
1.3.1 Introduction......Page 8309
1.3.2.1 Structural Types That May Donate Hydride......Page 8310
1.3.2.2 Some Mechanisms for Hydride Donation......Page 8311
1.3.2.3 Catalysis......Page 8312
1.3.3.1 Hydride Transfer from Formic Acid......Page 8314
1.3.3.2 Hydride Transfer from Aldehydes......Page 8316
1.3.3.3 Hydride Transfer from Alcohols and Amines......Page 8318
1.3.3.4 Hydride Transfer from Hydrocarbons......Page 8321
1.3.3.5 Hydride Transfer from Heterocycles......Page 8322
1.3.3.6 Hydride Transfer from Organometallics......Page 8328
1.3.4 References......Page 8333
1.4.1 Introduction......Page 8337
1.4.2.1 Early Mechanistic Studies......Page 8338
1.4.2.2 Reduction in the Absence of Proton Donors......Page 8339
1.4.2.3 Reduction in the Presence of Proton Donors......Page 8340
1.4.3.1 Reaction Medium......Page 8341
1.4.3.3 Chemoselectivity......Page 8343
1.4.3.4 Stereoselectivity......Page 8346
1.4.4.1 Reduction of Imines and Oximes......Page 8353
1.4.5 References......Page 8356
1.5.1 Introduction......Page 8358
1.5.2.1 Nonalkenic Ketones and Aldehydes......Page 8360
1.5.2.2 Alkenic and Alkynic Ketones and Aldehydes......Page 8363
1.5.3.1 Electroreduction of Acyclic and Cyclic Compounds with a C=N Bond......Page 8364
1.5.4 References......Page 8366
1.6.1 Introduction......Page 8368
1.6.2.1 Hydrogenation of Aldehydes......Page 8369
1.6.2.2 Hydrogenation of Ketones......Page 8370
1.6.3.2 Hydrogenation of Schiff's Bases (Aldimines and Ketimines)......Page 8372
1.6.4.1 Asymmetric Hydrogenation of the C=O Bond......Page 8373
1.6.4.2 Asymmetric Hydrogenation of the C=N Bond......Page 8374
1.6.5.1 Hydrogenation Using a Chirally Modified Catalyst......Page 8378
1.6.6.1 Homogeneous Hydrogenation by Rhodium or Other Complexes......Page 8381
1.6.7 References......Page 8384
1.7.2 Asymmetric Reductions of the Carbonyl Group......Page 8388
1.7.2.1 Chirally Modified Lithium Aluminum Hydride Reagents......Page 8389
1.7.2.3 Asymmetric Reduction with Chirally Modified Boranes and Alanes......Page 8399
1.7.2.4 Asymmetric Hydrosilylation......Page 8402
1.7.2.5 Asymmetric Reduction of the C=N Double Bond......Page 8405
1.7.4 References......Page 8409
1.8.1 Introduction......Page 8412
1.8.3 Sources of Enzymes and Microorganisms......Page 8413
1.8.6.1 Enantiomeric Distinctions......Page 8414
1.8.6.2 Enantiotopic Face Distinctions......Page 8416
1.8.6.3 Diastereotopic Face Distinctions......Page 8421
1.8.6.4 Combinations of Specificity......Page 8422
1.8.6.5 Preparations of Deuterated or Tritiated Alcohols......Page 8432
1.8.7 Reduction of C=N to CHNH......Page 8433
1.8.9 Future Developments......Page 8434
1.8.10 References......Page 8436
1.9.1 Introduction......Page 8439
1.9.2.2 Reduction with Dissolving Metals......Page 8440
1.9.2.3 Reduction with Metal Hydrides......Page 8441
1.9.3 Selective Reductions......Page 8444
1.9.3.1 Acyclic Ketals......Page 8445
1.9.3.2 Furanosides and Pyranosides......Page 8446
1.9.3.3 Spiroketals......Page 8448
1.9.3.4 Dioxolanes and Dioxanes......Page 8449
1.9.3.5 Bicyclic Acetals and Ketals......Page 8455
1.9.3.6 Azaacetals and Azaketals......Page 8456
1.9.3.7 Thioacetals and Thioketals......Page 8457
1.9.4 References......Page 8460
1.10 Reduction of Carboxylic Acid Derivatives to Alcohols, Ethers and Amines......Page 8463
1.10.1.2 Electrochemical and Dissolving Metal Reductions......Page 8464
1.10.1.3 Reductions Using Metal Hydride Reagents......Page 8465
1.10.2.1 Hydrogenation Reactions......Page 8467
1.10.2.3 Reductions Using Metal Hydride Reagents......Page 8468
1.10.3.2 Electrochemical and Dissolving Metal Reductions......Page 8470
1.10.3.3 Reductions Using Metal Hydride Reagents......Page 8472
1.10.4.1 Hydrogenation Reactions......Page 8474
1.10.4.3 Reductions Using Metal Hydride Reagents......Page 8475
1.10.5.2 Electrochemical and Dissolving Metal Reductions......Page 8476
1.10.5.3 Reductions Using Metal Hydride Reagents......Page 8477
1.10.6.1 Hydrogenation Reactions......Page 8479
1.10.6.2 Electrochemical and Dissolving Metal Reductions......Page 8480
1.10.6.3 Reductions Using Metal Hydride Reagents......Page 8481
1.10.8 References......Page 8482
1.11.1 Introduction......Page 8486
1.11.2 Carboxylic Acids......Page 8487
1.11.3 Acyl Halides......Page 8489
1.11.4 Esters of Carboxylic Acids (Including Ortho Esters)......Page 8493
1.11.5 Lactones......Page 8495
1.11.6 Amides of Carboxylic Acids......Page 8496
1.11.7 Lactams and Cyclic Imides......Page 8500
1.11.8 Nitriles......Page 8501
1.11.9 Miscellaneous Reductions to Aldehydes......Page 8502
1.11.10 Reviews and Books......Page 8505
1.11.11 References......Page 8506
1.12.1 Introduction......Page 8509
1.12.2 Carboxylic Acids......Page 8510
1.12.3 Acyl Chlorides......Page 8512
1.12.4 Carboxylic Acid Anhydrides......Page 8517
1.12.5 Carboxylic Acid Esters......Page 8518
1.12.7 Carboxylic Acid Amides......Page 8519
1.12.8 Nitriles......Page 8524
1.12.9 Imidoyl Chlorides......Page 8526
1.12.10 Amidines, Imidates and Thioimidates......Page 8528
1.12.11 Thioamides, Thioesters and Dithioesters......Page 8529
1.12.12 References......Page 8530
1.13.1 Introduction......Page 8532
1.13.2.1 Reduction with Alkali Metals in Liquid Ammonia......Page 8533
1.13.2.2 Clemmensen Reduction......Page 8534
1.13.3.1 Reduction with NaBH_4 , LiAIH_4 and Related Reagents......Page 8538
1.13.3.2 Reduction with BH_3 , DIBAL-H and Related Reagents......Page 8540
1.13.3.3 Ionic Hydrogenation......Page 8542
1.13.4.1 Catalytic Hydrogenation......Page 8544
1.13.4.2 Hydrogen Transfer Reduction......Page 8545
1.13.6 Miscellaneous......Page 8546
1.13.7 References......Page 8549
1.14 Reduction of C=X to CH_2 by Wolff-Kishner and Other Hydrazone Methods......Page 8551
1.14.2.1 General Procedures and Mechanistic Aspects......Page 8552
1.14.2.2 Modified Procedures......Page 8553
1.14.2.3 Scope and Limitations......Page 8562
1.14.3 Reduction of Aldehyde and Ketone Arylsulfonylhydrazones with Hydride Reagents......Page 8567
1.14.3.2 Reductions with Sodium Borohydride......Page 8569
1.14.3.3 Reductions with Sodium Cyanoborohydride......Page 8574
1.14.3.4 Reductions with Catechol Borane and Related Reagents......Page 8580
1.14.4 References......Page 8583
2.1.1 Introduction......Page 8587
2.1.3 Reduction of Aromatic Nitro and Nitroso Compounds to Azo and Azoxy Compounds......Page 8588
2.1.4 Reduction of Aromatic Nitro and Nitroso Compounds to Hydroxylamines......Page 8590
2.1.5.1 Transfer Hydrogenation......Page 8591
2.1.5.2 Borohydride and Borane Reductions......Page 8593
2.1.5.3 Reductions Involving Tellurium, Selenium and Sulfur......Page 8594
2.1.5.4 Transition Metal Reductions......Page 8595
2.1.5.6 Carbon Monoxide......Page 8596
2.1.6 Reduction of Aliphatic Nitro Compounds to Hydroxylamines......Page 8597
2.1.7.1 Nitroalkane Reductions......Page 8598
2.1.7.2 Nitroalkene Reductions......Page 8599
2.1.8 References......Page 8601
2.2.1 Introduction......Page 8604
2.2.2.1 Reduction to N-N Bonded Groups......Page 8605
2.2.2.2 Reductive Cleavage......Page 8606
2.2.3.1 Cleavage of Hydrazones......Page 8610
2.2.3.2 Cleavage of Hydrazines, Hydrazides and N-Nitrosamines......Page 8611
2.2.4.2 Deoxygenation of Nitrones, Nitrile Oxides and Tertiary Amine Oxides......Page 8613
2.2.4.3 Reduction of Oximes to Imines......Page 8615
2.2.4.4 Reduction of Hydroxylamines to Amines......Page 8617
2.2.5.3 Reduction of Disubstituted Peroxides......Page 8619
2.2.5.4 Reductive Ozonolysis of Alkenes......Page 8621
2.2.6 References......Page 8622
2.3.1 Introduction......Page 8626
2.3.2.1 Reduction (Deoxygenation) of Sulfoxides......Page 8627
23.2.2 Reduction of Sulfones......Page 8630
2.3.2.3 Reduction of Sulfonic and Sulfinic Acids and Their Derivatives......Page 8631
2.3.2.4 Reduction of Sulfimides (Sulfilimines) and Sulfoximides (Sulfoximines)......Page 8632
2.3.2.5 Reduction of Se and Te Analogs......Page 8633
2.3.3 Reduction of P=O Compounds......Page 8634
2.3.4.1 Reduction of Disulfides and Diselenides......Page 8635
2.3.5 References......Page 8636
3.1 Heterogeneous Catalytic Hydrogenation of C=C and C tbond C......Page 8639
3.1.1.2 Catalysts......Page 8640
3.1.2.2 Kinetics......Page 8641
3.1.2.3 Mechanism......Page 8642
3.1.3 Hydrogenation of C=C......Page 8643
3.1.3.1 Double Bond Migration......Page 8644
3.1.3.2 Structure - Reactivity......Page 8646
3.1.3.3 Stereochemistry......Page 8648
3.1.3.4 Haptophilicity......Page 8651
3.1.4.1 Semihydrogenation......Page 8652
3.1.4.2 Mechanism......Page 8653
3.1.4.3 Regio- and Stereo-Selectivity......Page 8654
3.1.5.3 Conjugated Diene Mechanisms......Page 8655
3.1.5.4 Allenes and Cumulenes......Page 8656
3.1.6.1 Structure - Reactivity......Page 8658
3.1.6.3 Stereochemistry......Page 8659
3.1.7.1 Regioselectivity......Page 8660
3.1.8.2 Conjugated Functional Groups......Page 8661
3.1.10 References......Page 8662
3.2.1 Hydrogenation of Nonconjugated C=C Bonds......Page 8665
3.2.2.2 Dienes and Trienes to Alkenes by 1,2-Reduction......Page 8671
3.2.2.3 Dienes to Alkenes by 1,4-Reduction......Page 8673
3.2.2.4 Hydrogenation of C=C Bonds Conjugated with Aromatic Rings, CN, CO, CO_2 R, etc.......Page 8674
3.2.3 Hydrogenation of Aromatic and Heteroaromatic Rings......Page 8675
3.2.4.1 Reduction of C tbond C Bonds to Saturated Hydrocarbons......Page 8678
3.2.4.3 Reduction of C tbond C Bonds to cis-Alkenes......Page 8679
3.2.4.4 Reduction of C tbond C Bonds to trans-Alkenes......Page 8680
3.2.5.1 Chiral Catalysts......Page 8681
3.2.5.2 Asymmetric Hydrogenation of Enamides and Related Substrates......Page 8682
3.2.5.3 Asymmetric Hydrogenation of Acrylic Acids and Esters......Page 8683
3.2.5.4 Asymmetric Hydrogenation of Allylic Alcohols......Page 8684
3.2.6 References......Page 8685
3.3.1 Introduction......Page 8692
3.3.2.3 Mechanism of Reduction by Diimide......Page 8693
3.3.2.4 Scope and Limitations......Page 8697
3.3.3.2 Mechanisms of Dissolving Metal Reductions......Page 8699
3.3.3.3 Scope and Limitations......Page 8700
3.3.4.1 Introduction......Page 8702
3.3.4.2 Mechanism of the Reduction of C=C and C tbond C by Cr^II......Page 8703
3.3.5.2 Mechanism of Metal Hydride - Transition Metal Halide Reductions......Page 8704
3.3.5.3 Scope and Limitations......Page 8706
3.3.6.2 Mechanism of the Ionic Hydrogenation Reaction......Page 8707
3.3.7 References......Page 8708
3.4 Partial Reduction of Aromatic Rings by Dissolving Metals and by Other Methods......Page 8710
3.4.2 The Birch Reduction......Page 8711
3.4.2.1 Experimental Procedures......Page 8713
3.4.3.1 Benzenoid Hydrocarbons and Ethers......Page 8714
3.4.3.3 Biphenyls, Fluorenes and Fused Polycyclic Hydrocarbons......Page 8717
3.4.3.4 Phenols......Page 8718
3.4.3.5 Aromatic Amines......Page 8719
3.4.3.6 Carboxylic Acids......Page 8720
3.4.3.7 Aromatic Carboxylic Esters......Page 8726
3.4.3.8 Aromatic Amides......Page 8728
3.4.3.9 Aromatic Ketones......Page 8729
3.4.3.10 Aryl- and Benzyl-Silanes......Page 8734
3.4.3.11 Hydrogenolysis during Birch Reductions......Page 8735
3.4.4.1 The Benkeser Reduction......Page 8737
3.4.4.4 Reductive Silylations......Page 8738
3.4.4.5 Organometallic Procedures......Page 8739
3.4.5 References......Page 8740
3.5 Partial Reduction of Enones, Styrenes and Related Systems......Page 8743
3.5.2.1 Dissolving Metal Reduction......Page 8744
3.5.2.2 Reduction with Low-Valent Transition Metals......Page 8751
3.5.2.3 Electrochemical Reduction......Page 8752
3.5.3 Catalytic Hydrogenation......Page 8753
3.5.4.1 Boron Hydrides......Page 8756
3.5.4.2 Aluminum Hydrides......Page 8761
3.5.4.3 Silicon Hydrides......Page 8766
3.5.4.4 Tin Hydrides......Page 8767
3.5.5.1 Copper Hydrides......Page 8768
3.5.5.2 Iron Hydrides......Page 8770
3.5.6.1 Transfer Hydrogenation Using Alcohols as Hydrogen Donors......Page 8771
3.5.6.2 Transition Metal Catalyzed Reductions with Group 14 Metal Hydrides......Page 8773
3.5.6.3 Transition Metal Catalyzed Reductions with Other Hydrogen Donors......Page 8777
3.5.7.1 Enzymatic Reductions......Page 8778
3.5.7.2 Biomimetic Reductions with NAD(P)H Models......Page 8781
3.5.8 Miscellaneous Reducing Agents......Page 8783
3.5.9.1 Dissolving Metal Reduction......Page 8784
3.5.9.2 Catalytic Hydrogenation......Page 8785
3.5.9.3 Miscellaneous Reducing Agents......Page 8788
3.5.10 References......Page 8789
3.6.2.1 Metal Hydride Reductions......Page 8799
3.6.2.3 Reduction with Sodium Dithionite......Page 8809
3.6.2.4 Reduction with Formic Acid......Page 8810
3.6.2.5 One-Electron Reduction......Page 8811
3.6.3 Hydrogenation......Page 8817
3.6.4 References......Page 8820
3.7 Partial and Complete Reduction of Pyrroles, Furans, Thiophenes and Their Benzo Analogs......Page 8823
3.7.2.1 Catalytic Hydrogenation......Page 8824
3.7.2.2 Dissolving Metals and Metals in Acid......Page 8825
3.7.3.1 Catalytic Hydrogenation......Page 8826
3.7.3.2 Dissolving Metals......Page 8827
3.7.4.1 Catalytic Hydrogenation......Page 8828
3.7.4.2 Dissolving Metals......Page 8829
3.7.4.3 Ionic Hydrogenation......Page 8830
3.7.4.5 Miscellaneous Methods......Page 8831
3.7.5.1 Catalytic Hydrogenation......Page 8832
3.7.5.2 Dissolving Metals and Metals in Acid......Page 8834
3.7.5.3 Boron Hydrides and Related Methods......Page 8836
3.7.6 Reduction of Benzo[b]Furans......Page 8844
3.7.6.1 Catalytic Hydrogenation......Page 8845
3.7.6.2 Dissolving Metals......Page 8846
3.7.6.3 Boron Hydrides and Related Methods......Page 8847
3.7.6.4 Miscellaneous Methods......Page 8848
3.7.7.2 Dissolving Metals......Page 8849
3.7.8 References......Page 8850
3.8 Partial and Complete Reduction of Heterocycles Containing More Than One Heteroatom......Page 8854
3.8.2.1 Five-Membered Ring Systems......Page 8855
3.8.2.2 Six-Membered Ring Systems......Page 8859
3.8.3.1 Five-Membered Ring Systems......Page 8863
3.8.3.2 Six-Membered Ring Systems......Page 8871
3.8.4.1 Five-Membered Ring Systems......Page 8875
3.8.4.2 Six-Membered Ring Systems......Page 8877
3.8.5.1 Dioxolanes, Dioxanes, Dithioles and Benzodithioles......Page 8878
3.8.6.1 Triazoles, Triazolium Salts and Benzotriazoles......Page 8880
3.8.7.1 Oxadiazoles and Benzoxadiazoles......Page 8882
3.8.8 References......Page 8883
3.9.1 Introduction......Page 8886
3.9.2 Mechanistic Aspects......Page 8887
3.9.2.1 Thermodynamic Considerations......Page 8888
3.9.2.2 Detailed Mechanism of Hydrometallation......Page 8890
3.9.3.1 Synthesis, Structure and Properties of Reagents......Page 8894
3.9.3.2 Hydrozirconation of Alkenes and Alkynes......Page 8895
3.9.3.3 Selectivity Issues......Page 8902
59299_v08_03_09b.pdf......Page 8908
3.9.3.4 Synthetic Utilization of Hydrozirconation......Page 8909
3.9.4.1 Hydrometallation with Other Transition Metals......Page 8914
3.9.4.2 Catalytic Hydrometallation with Main Group Metals......Page 8916
3.9.5 References......Page 8918
3.10.1.1 Introduction......Page 8922
3.10.1.2 Fundamentals of the Hydroboration Reaction......Page 8923
3.10.2.1 Hydroboration with Boran - Tetrahydrofuran......Page 8924
3.10.2.2 Hydroboration with Other Sources of Borane......Page 8927
3.10.3.1 Hydroboration with Thexylborane and Other Alkyl- and Aryl-Boranes......Page 8928
3.10.3.2 Hydroboration with Monohaloboranes......Page 8929
3.10.4.1 General Considerations......Page 8931
3.10.4.2 Hydroboration with 9-BBN-H......Page 8932
3.10.4.3 Hydroboration with Other Dialkyl- and Diaryl-Boranes......Page 8934
3.10.4.4 Hydroboration with Dihaloboranes......Page 8937
3.10.4.6 Hydroboration with Catecholborane and Related Compounds......Page 8938
3.10.5.1 General Considerations......Page 8939
3.10.5.2 Survey of Reactions......Page 8940
3.10.7.1 General Considerations......Page 8943
3.10.7.2 Protonolysis of Alkylboranes with Carboxylic Acids: Synthesis of Alkanes......Page 8944
3.10.7.3 Protonolysis of Alkenylboranes: Synthesis of Alkenes and Dienes......Page 8945
3.10.8 References......Page 8946
3.11 Hydroalumination of C=C and C tbond C......Page 8951
3.11.1.2 Historical Context and Development......Page 8952
3.11.1.3 Sources of the Aluminum Hydrides......Page 8954
3.11.1.5 Potential of Resulting Organoaluminum Reagents in Organic Synthesis......Page 8955
3.11.2.1 Suitable Alkenic Substrates......Page 8957
3.11.2.2 Suitable Alkynic Substrates......Page 8958
3.11.2.4 Interfering Functional Groups......Page 8960
3.11.2.6 Selectivity......Page 8962
3.11.2.7 Modifications in the Hydroalumination Process......Page 8964
3.11.3.1 Reaction Rates and Kinetic Rate Expressions......Page 8965
3.11.3.2 Substituent Effects on Relative Rates of Alkynes......Page 8967
3.11.3.4 Stereochemical Effects of Lewis Acids and Bases......Page 8968
3.11.3.5 Kinetic Effects of Transition Metals......Page 8969
3.11.4.1 Experimental Conditions: Protolysis and Oxidation......Page 8971
3.11.4.3 Metallodealumination......Page 8972
3.11.4.4 Carbodealumination......Page 8973
3.11.4.5 Carbalurnination......Page 8974
3.11.5.1 Dienes, Polyenes and Enynes......Page 8975
3.11.5.3 Carbocyclizations......Page 8976
3.11.6 References......Page 8977
3.12.1 Introduction......Page 8980
3.12.1.1 Catalysts......Page 8981
3.12.1.4 Mechanism......Page 8982
3.12.2.1 Hydrosilylation of Acetylene......Page 8986
3.12.2.2 Hydrosilylation of Monosubstituted Alkynes......Page 8987
3.12.2.3 Hydrosilylation of Disubstituted Alkynes......Page 8988
3.12.3 Hydrosilylation of Conjugated Carbon-Carbon Triple Bonds......Page 8989
3.12.4.1 Hydrosilylation of Ethylene......Page 8990
3.12.4.2 Hydrosilylation of Monosubstituted Alkenes......Page 8991
3.12.4.3 Hydrosilylation of Disubstituted and More Highly Substituted Alkenes......Page 8993
3.12.5.1 Hydrosilylation of Acyclic Polyenes......Page 8995
3.12.5.2 Hydrosilylation of Cyclic Polyenes......Page 8997
3.12.6 Hydrosilylation of Conjugated Enones......Page 8998
3.12.7 Asymmetric Hydrosilylation of Carbon-Carbon Double Bonds......Page 8999
3.12.8.1 Reaction of Vinylsilanes with Electrophiles......Page 9002
3.12.8.4 Aldol Reactions......Page 9003
3.12.8.5 Synthetic Reactions of Pentafluorosilicates......Page 9004
3.12.8.7 Hydrosilylation in the Presence of CO......Page 9005
3.12.9 References......Page 9006
4.1.1 Introduction and Scope of the Review......Page 9010
4.1.3 Catalytic Hydrogenolysis......Page 9011
4.1.4.1 Reductions with Metals (Dissolving Metal Method)......Page 9012
4.1.4.2 Reduction with Low-Valent Metal Salts......Page 9013
4.1.5.1 Tributyltin Hydride......Page 9015
4.1.5.3 Other Metal Hydride Reagents......Page 9018
4.1.6.1 Reduction with LiAlH_4......Page 9019
4.1.6.3 Sodium Borohydride......Page 9020
4.1.6.4 Lithium Triethylborohydride......Page 9021
4.1.7 Miscellaneous Reduction Procedures......Page 9023
4.1.8 References......Page 9024
4.2.1 Introduction......Page 9027
4.2.2.1 Hydride Reduction Methods......Page 9028
4.2.2.2 Catalytic Hydrogenolysis......Page 9030
4.2.2.3 Electron Transfer Reductions......Page 9031
4.2.2.4 Stannane Reduction of O-Thiocarbonyl Derivatives......Page 9034
4.2.2.5 Stannane and Silane Reduction of Esters and Carbonates......Page 9040
4.2.3.1 Hydride and Hydrogenolysis Methods......Page 9042
4.2.3.2 Deamination via Diazenes and Related Species......Page 9044
4.2.3.3 Reduction of Isonitriles and Related Compounds......Page 9046
4.2.4 References......Page 9048
4.3.1.1 Introduction......Page 9050
4.3.1.2 Raney Nickel and Nickel(0) Complexes......Page 9051
4.3.1.3 Hydrides or Organometallics Combined with Transition Metal Salts or Their Complexes......Page 9054
4.3.1.4 Metals and Amalgams......Page 9057
4.3.1.5 Tin Hydrides......Page 9060
4.3.2.2 Raney Nickel......Page 9062
4.3.2.4 Alkali Metals......Page 9063
4.3.2.6 Miscellaneous Deselenations......Page 9064
4.3.3.1 Protonolysis......Page 9065
4.3.3.2 Metal Hydride Demercuration......Page 9066
4.3.3.3 Miscellaneous Methods......Page 9072
4.3.4.1 Reduction of Tervalent Organophosphorus Compounds......Page 9073
4.3.4.2 Reduction of Tetravalent Organophosphorus Compounds......Page 9075
4.3.4.3 Reduction of Pentavalent Organophosphorus Compounds......Page 9078
4.3.5 References......Page 9080
4.4.2 Reduction of Epoxides to Alcohols......Page 9086
4.4.2.1 Metal Hydrides......Page 9087
4.4.2.2 Dissolving Metals......Page 9095
4.4.2.3 Hydrogenolysis......Page 9096
4.4.2.4 Miscellaneous......Page 9098
4.4.3 Deoxygenation of Epoxides......Page 9099
4.4.3.1 Phosphorus Reagents......Page 9100
4.4.3.2 Silicon and Tin Reagents......Page 9101
4.4.3.3 Selenium and Tellurium Reagents......Page 9102
4.4.3.4 Low-Valent Metals......Page 9103
4.4.3.6 Miscellaneous......Page 9105
4.4.4 References......Page 9106
4.5.1 Hydrogenolysis of the Carbon-Halogen Bond in Vinyl Halides......Page 9109
4.5.1.1 Hydrogenolysis of Vinylic Fluorides......Page 9110
4.5.1.2 Hydrogenolysis of Vinylic Chlorides......Page 9111
4.5.1.3 Hydrogenolysis of Vinylic Bromides......Page 9113
4.5.1.4 Hydrogenolysis of Vinylic Iodides......Page 9114
4.5.2.1 General......Page 9115
4.5.2.2 Hydrogenolysis of Aryl Fluorides......Page 9117
4.5.2.3 Hydrogenolysis of Aryl Chlorides......Page 9118
4.5.2.4 Hydrogenolysis of Aryl Bromides......Page 9120
4.5.2.5 Hydrogenolysis of Aryl Iodides......Page 9122
4.5.3.2 Hydrogenolysis of Phenols and Their Derivatives......Page 9124
4.5.4 Hydrogenolysis of Trigonal Carbon-Sulfur Bonds......Page 9127
4.5.5.1 Hydrogenolysis of Enamines......Page 9129
4.5.5.3 Hydrogenolysis of Arenediazonium Salts......Page 9130
4.5.6 References......Page 9135
4.6.1 Introduction......Page 9137
4.6.3 Reduction and Subsequent Dehydration......Page 9138
4.6.4 Reductive Elimination of alpha-Substituted Ketones......Page 9139
4.6.5.1 Vinyl Esters......Page 9144
4.6.5.2 Vinyl Ethers......Page 9148
4.6.5.3 Vinyl Halides......Page 9151
4.6.5.4 Enamines......Page 9152
4.6.6 Reductive Elimination of Hydrazone Derivatives......Page 9153
4.6.6.1 Formation of Arenesulfonylhydrazones......Page 9154
4.6.6.2 The Aprotic Bamford-Stevens Reaction......Page 9155
4.6.6.3 The Protic Bamford-Stevens Reaction......Page 9157
4.6.6.4 The Shapiro Reaction......Page 9158
4.6.7.1 Quinones to Arenes......Page 9163
4.6.7.2 Ketones and 1,2-Diketones to Alkynes......Page 9164
4.6.8 References......Page 9165
4.7.1 Introduction......Page 9168
4.7.2.1 Hydrogenolysis over Palladium with Molecular Hydrogen......Page 9169
4.7.2.2 Hydrogenolysis over Palladium with Other Hydride Sources......Page 9171
4.7.2.4 Hydrogenolysis over Raney Nickel......Page 9176
4.7.3.1 Lithium Aluminum Hydride......Page 9178
4.7.3.3 Sodium Borohydride......Page 9180
4.7.3.5 Other Hydride Reducing Agents......Page 9182
4.7.4.1 Lithium and Sodium in Liquid Ammonia......Page 9184
4.7.4.2 Other Metals......Page 9185
4.7.5 Electrolytic Reduction Processes......Page 9187
4.7.6 Biomimetic Reducing Agents......Page 9190
4.7.8 Miscellaneous Reducing Agents......Page 9191
4.7.9 References......Page 9192
4.8 Reduction of alpha-Substituted Carbonyl Compounds-CX-CO-to Carbonyl Compounds-CH-CO-......Page 9195
4.8.1.2 Mechanisms of Bond Cleavage......Page 9196
4.8.2.1 Reduction by Electron Transfer......Page 9197
4.8.2.2 Reduction by Strong Nucleophiles......Page 9200
4.8.3.1 Reduction by Electron Transfer......Page 9203
4.8.4.1 Reduction by Electron Transfer......Page 9205
4.8.6 The Carbon-Carbon Bond......Page 9207
4.8.8 References......Page 9208
A......Page 9210
B......Page 9213
C......Page 9219
D......Page 9223
E......Page 9226
F......Page 9227
G......Page 9230
H......Page 9234
59299_v08_aindxb.pdf......Page 9238
I......Page 9239
J......Page 9240
K......Page 9242
L......Page 9247
M......Page 9250
N......Page 9257
O......Page 9260
P......Page 9262
R......Page 9265
59299_v08_aindxc.pdf......Page 9266
S......Page 9269
T......Page 9277
V......Page 9281
W......Page 9283
Y......Page 9286
Z......Page 9288
A......Page 9289
B......Page 9296
C......Page 9302
D......Page 9309
E......Page 9312
F......Page 9314
G......Page 9315
H......Page 9316
I......Page 9319
K......Page 9322
L......Page 9324
M......Page 9326
N......Page 9327
O......Page 9329
P......Page 9331
Q......Page 9337
R......Page 9338
S......Page 9340
T......Page 9344
V......Page 9347
Z......Page 9348
Front Matter......Page 9350
Table of Contents......Page 9352
Preface......Page 9353
Contents of All Volumes......Page 9355
A......Page 9362
B......Page 9375
59299_v09_caindxb.pdf......Page 9387
C......Page 9406
59299_v09_caindxc.pdf......Page 9413
D......Page 9428
59299_v09_caindxd.pdf......Page 9437
E......Page 9444
F......Page 9451
59299_v09_caindxe.pdf......Page 9463
G......Page 9464
H......Page 9482
59299_v09_caindxf.pdf......Page 9489
I......Page 9507
59299_v09_caindxg.pdf......Page 9513
J......Page 9514
K......Page 9522
59299_v09_caindxh.pdf......Page 9539
L......Page 9550
59299_v09_caindxi.pdf......Page 9565
M......Page 9567
59299_v09_caindxj.pdf......Page 9589
N......Page 9600
O......Page 9612
59299_v09_caindxk.pdf......Page 9613
P......Page 9622
59299_v09_caindxl.pdf......Page 9638
Q......Page 9640
R......Page 9641
S......Page 9658
S 303-326......Page 9664
59299_v09_caindxn.pdf......Page 9688
T......Page 9701
59299_v09_caindxo.pdf......Page 9712
U......Page 9719
V......Page 9723
W......Page 9731
59299_v09_caindxp.pdf......Page 9738
X......Page 9749
Y......Page 9750
Z......Page 9757
A......Page 9761
59299_v09_csindxb.pdf......Page 9792
B......Page 9816
59299_v09_csindxc.pdf......Page 9824
C......Page 9850
C 497-528......Page 9857
59299_v09_csindxe.pdf......Page 9889
D......Page 9904
59299_v09_csindxf.pdf......Page 9921
E......Page 9925
F......Page 9943
G......Page 9951
59299_v09_csindxg.pdf......Page 9955
H......Page 9958
I......Page 9973
59299_v09_csindxh.pdf......Page 9988
J......Page 9990
K......Page 9991
L......Page 10001
M......Page 10013
59299_v09_csindxi.pdf......Page 10021
N......Page 10027
O......Page 10038
P......Page 10053
P 695-726......Page 10055
59299_v09_csindxk.pdf......Page 10087
Q......Page 10095
R......Page 10098
S......Page 10105
59299_v09_csindxl.pdf......Page 10121
T......Page 10135
59299_v09_csindxm.pdf......Page 10154
U......Page 10158
V......Page 10160
W......Page 10164
X......Page 10166
Y......Page 10167
Z......Page 10168