Comprehensive Organic Functional Group Transformations II: v. 2(Carbon with One Heteroatom Attached by a Single Bond)

Cover Page......Page 1
Book Info......Page 2
Editors-in-Chief......Page 3
Editor of Volume 2......Page 5
Editor of Volume 4......Page 6
Editor of Volume 6......Page 7
Preface......Page 8
Introduction to Volume 2......Page 9
Explanation of the reference system......Page 10
Journal Abbreviations......Page 11
Techniques/Conditions......Page 13
Reagents, Solvents, etc.......Page 14
Part I: Tetracoordinated Carbon with No Attached Heteroatoms......Page 17
Part II: Tricoordinated Carbon with No Attached Heteroatoms......Page 18
Part III: Dicoordinate and Monocoordinate Carbon with No Attached Heteroatoms......Page 19
2.01 Alkyl Halides......Page 20
Alkyl Halides from Alkenes......Page 21
Alkyl Halides from Alcohols and Their Derivatives......Page 22
Alkyl Halides from Amines and Their Derivatives......Page 24
Alkyl Fluorides from Alkanes......Page 25
Alkyl Fluorides from Alkenes......Page 26
Alkyl Fluorides from Alcohols and Their Derivatives......Page 27
Alkyl Chlorides from Alkanes......Page 28
Alkyl Chlorides from Alcohols and Their Derivatives......Page 29
Alkyl Chlorides from Amines and Their Derivatives......Page 30
Alkyl Bromides from Alkenes......Page 31
Alkyl Bromides from Alcohols and Their Derivatives......Page 32
Alkyl Iodides from Alkanes......Page 33
Alkyl Iodides from Alkyl Halides......Page 34
Alkyl Iodides by Iododecarboxylation of Carboxylic Acids and Their Derivatives......Page 35
References......Page 36
Biographical sketch......Page 40
2.02 Alkyl Chalcogenides: Oxygen-based Functional Groups......Page 42
From Biotransformations......Page 43
By Addition to Alkenes......Page 46
Substrate control in osmylation......Page 47
Asymmetric dihydroxylation......Page 49
Asymmetric aminohydroxylation......Page 52
Hydrogenation using heterogeneous catalysis......Page 53
Asymmetric hydrogenation under homogeneous catalysis......Page 54
Reduction using carbon hydrides......Page 55
Reduction using metal hydrides: Miscellaneous......Page 57
Pinacol couplings......Page 58
Others......Page 59
Asymmetric LiAlH4 modifications......Page 60
Oxazaborolidines......Page 62
Asymmetric borohydride modifications......Page 63
Organozinc and organocopper reagents......Page 65
Via organolithiums......Page 66
Via organozincs......Page 67
Via organoborons......Page 70
Nucleophilic allylation......Page 71
Allylation using boranes, silanes, and stannanes......Page 72
By heteroatomic nucleophiles......Page 75
By carbon nucleophiles......Page 77
Oxetanes......Page 78
Others......Page 79
General methods......Page 80
Methyl ethers......Page 82
Direct synthesis......Page 83
Indirect syntheses......Page 87
Indirect Synthesis......Page 89
Tetrahydropyrans......Page 91
Dihydropyrans......Page 92
Miscellaneous......Page 93
From alkyl halides and oxygen......Page 95
From oxazol-5(4H)-inones......Page 96
O-Alkylhydroxylamines, RONH2......Page 97
Trialkyl phosphates......Page 98
References......Page 99
Biographical sketch......Page 107
2.03 Alkyl Chalcogenides: Sulfur-based Functional Groups......Page 108
Formation from Alkenes......Page 111
Formation from Alcohols......Page 114
Formation Using Phosphorothiolate Ion......Page 117
Formation via Isothiouronium Salts and Related Procedures......Page 118
Formation via Bunte Salts......Page 119
Formation via Xanthates and Related Esters......Page 120
Formation Using Sulfur Insertion Reactions of Organometallics......Page 121
Formation from Sulfonyl Halides and Other Sulfonic Acid Derivatives......Page 122
Formation by Reductive Cleavage of Disulfides......Page 123
Formation from Thiocyanates......Page 124
Formation by Dealkylation (Carbon-Sulfur Bond Cleavage) of Sulfides......Page 125
Formation by Heterocyclic Ring Cleavage......Page 127
Formation from Aldehydes, Ketones, and Carboxylic Acid Derivatives......Page 130
Miscellaneous......Page 132
Formation from alkyl halides and alkyl thiolates......Page 133
Formation from alcohols......Page 135
Formation from epoxides......Page 137
Formation from electron-deficient alkenes......Page 139
Formation from carbonyl compounds......Page 141
Formation from thiocarbonyl compounds......Page 142
Formation from thioacetals......Page 143
Formation from sulfoxides......Page 144
Formation from disulfides......Page 145
Formation from sulfonium salts......Page 146
Formation from alpha-sulfenyl anions......Page 147
Hydrogen peroxide......Page 148
Organic peroxides and hydroperoxides......Page 149
Halogens and halogen compounds......Page 150
Other chemical oxidants......Page 151
Reduction of sulfones......Page 152
Sulfinyl group transfer......Page 153
From sulfinic acids and their derivatives......Page 154
Via alpha-sulfonyl carbanions......Page 156
Rearrangement......Page 157
The reaction of sulfides with N-halo compounds......Page 158
The reaction of sulfides with hydroxylamine derivatives......Page 159
Sulfimino group transfer......Page 160
From sulfoxides......Page 161
Alkanesulfenyl fluorides......Page 162
Alkanesulfenyl chlorides......Page 163
Alkanesulfenyl iodides......Page 166
Alkanesulfinyl Halides......Page 167
Alkanesulfonyl Halides......Page 168
Oxidation of sulfur-containing moieties......Page 169
Preparations of sulfonyl halides from other sulfur(VI) functionality......Page 170
Thermolysis of sulfoxides......Page 173
Reaction of organometallics with sulfur dioxide......Page 174
Hydrolysis of sulfinic acid derivatives......Page 175
Reductive cleavage......Page 176
With sulfur trioxide......Page 177
With hydrogen sulfite ion and sulfites......Page 178
From thiols, disulfides, and related compounds......Page 179
From sulfonic acid derivatives......Page 180
From sulfinyl halides......Page 181
From thiosulfonates......Page 182
From sulfinamides......Page 183
From unsaturated alcohols......Page 184
From a sulfamidite......Page 185
From sulfonyl halides......Page 186
From sulfonic acids......Page 187
From sulfonamides......Page 189
From sulfones......Page 190
From unsaturated sulfonic esters......Page 191
From sulfonyl esters......Page 192
X=Sulfur......Page 193
X=Nitrogen......Page 194
X=Silicon......Page 195
Oxidation of thiols......Page 196
Peroxides......Page 197
Oxidation by metal ions/metal oxides......Page 198
Miscellaneous methods for the oxidation of thiols to disulfides......Page 199
With disulfides......Page 200
By reaction of alkenes with sulfenylating agents......Page 201
Via ring opening and coupling of thiiranes......Page 202
Sodium borohydride trisulfide (sulfurated sodium borohydride) and other borohydride trisulfides......Page 203
Sulfenyl halides......Page 204
Alkanethiosulfinates and Thiosulfonates......Page 205
Sulfenyl Selenides......Page 206
Higher-coordinated RSSe Functionality......Page 207
From sulfenyl halides......Page 208
From thiols......Page 209
From disulfides......Page 210
Miscellaneous......Page 211
From sulfenamides......Page 212
Miscellaneous methods of alkanesulfinamide preparation......Page 213
From other sulfur(VI) functionality......Page 214
Miscellaneous methods......Page 218
From thiols......Page 219
From alkyl halides......Page 222
From disulfides......Page 223
By rearrangement......Page 224
From thiocyanates......Page 225
From sulfonyl chlorides and sulfonic acids......Page 226
From aminoarsines......Page 227
Alkanethiosilanes......Page 228
Boranes and haloboranes......Page 229
RS-Metal Functions and their Higher-Coordinated Derivatives......Page 230
M=Potassium......Page 231
M=Mercury......Page 232
M=Tin......Page 233
M=Aluminum......Page 234
M=Iron......Page 235
M=Nickel, Palladium, and Platinum......Page 236
References......Page 237
Biographical sketch......Page 254
Alkaneselenols (RSeH) and Alkanetellurols (RTeH)......Page 256
Alkyl Selenides and Alkyl Tellurides......Page 257
Alkyl Selenoxides and Alkyl Telluroxides......Page 261
Alkyl Selenonium Salts and Alkyl Telluronium Salts......Page 262
Alkyl Selenocyanates (RSeCN) and Alkyl Tellurocyanates (RTeCN)......Page 263
Alkaneseleninic Acids and Alkanetellurinic Acids......Page 264
Alkyl Diselenides (R1SeSeR2) and Alkyl Ditellurides (R1TeTeR2)......Page 265
RSeP, RSeAs, RSeSb, and RSeBi Functions and their Higher-Coordinated Analogs, and Corresponding Tellurium Compounds......Page 268
RSeSi, RSeGe, RSeB, and Related Metalloid Functions and their Higher-Coordinated Derivatives, and Corresponding Tellurium Compounds......Page 269
References......Page 270
Biographical sketch......Page 273
2.05 Alkylnitrogen Compounds: Amines and Their Salts......Page 274
Use of Ammonia and Amines......Page 275
Alkylation at Nitrogen......Page 276
Deprotection......Page 279
Miscellaneous......Page 280
Amines from Alkenes and Alkynes......Page 281
Amines from Hydroxyl Compounds and Their Derivatives......Page 282
Amines from Aldehydes and Ketones......Page 284
By reduction......Page 287
By addition of an organometallic reagent......Page 289
By addition of other carbon nucleophiles......Page 292
Amines from Oximes and Their Derivatives......Page 293
Amines from Iminium Salts......Page 294
Amines from Azides......Page 295
Amines from Aziridines......Page 296
Amines from Amides......Page 297
Amines from Other Functional Groups......Page 298
Aziridines......Page 299
Pyrrolidines......Page 302
Pyrrolines......Page 305
Pyrrolizidines......Page 306
Piperidines......Page 307
Miscellaneous......Page 309
References......Page 310
Biographical sketch......Page 319
2.06 Alkylnitrogen Compounds: Compounds with N-Halogen, N-O, N-S, N-Se, and N-Te Functional Groups......Page 320
N-Fluoroalkylamines: RNHF, R2NF, RNF2, R3N+F......Page 321
Primary and secondary N-fluoroalkylamines: RNHF, R2NF......Page 322
Primary and secondary N-chloroalkylamines: RNHCl, R2NCl......Page 323
N,N-Dichloroalkylamines: RNCl2......Page 324
Reductive methods......Page 325
Reductive methods......Page 326
Nucleophilic addition to nitrones......Page 327
From addition of alkyllithium reagents to nitrones......Page 328
From rearrangements......Page 329
From radical addition to oxime ethers......Page 330
By C-N bond formation......Page 331
Intramolecular cycloaddition of oximes......Page 332
From C-N bond formation......Page 333
O-Alkylation of nitrones and nitroxides......Page 335
1,3-Dipolar addition of nitrones to alkenes......Page 336
Cycloaddition of N-oxides to alkenes......Page 337
From addition of siloxy amines to alkenes......Page 338
N-Aluminumoxyamines: R2NOAlAlk2......Page 339
Primary sulfenamides: R1NHSR2......Page 340
Sulfenamide salts: R13N+SR2, R12N-S+R22......Page 341
Derivatives of sulfinamides......Page 342
From phosphorylation of sulfinimines......Page 343
From reactions with Grignard and alkyllithium reagents......Page 345
Sulfonamides: R1NHSO2R2, R12NSO2R2......Page 346
From N-sulfonylaziridines and other ring-opening reactions......Page 347
From sulfonimines......Page 348
Other specific methods......Page 349
N-Substituted Sulfonamides: R1N(X)SO2R2......Page 350
Sulfamoyl halides: R1R2NSO2X......Page 351
References......Page 352
Biographical sketch......Page 360
2.07 Alkylnitrogen Compounds: Compounds with N-N, N-P, N-As, N-Sb, N-Bi, N-Si, N-Ge, N-B, and N-Metal Functional Groups......Page 362
By alkylation......Page 364
By miscellaneous methods......Page 365
By reduction of hydrazones and hydrazides......Page 366
By alkylation......Page 367
By miscellaneous methods......Page 368
By addition of organometallic reagents to hydrazones......Page 369
By miscellaneous methods......Page 370
By reduction and reductive alkylation of hydrazides and hydrazones......Page 371
Ammonium imides and amine-imines......Page 372
N-Nitrosoamines and N-thionitrosoamines......Page 373
Miscellaneous hydrazine derivatives......Page 374
Tetrazanes and tetrazenes......Page 375
Compounds with an N-P Bond......Page 376
Bis(dialkylamino)chlorophosphines, (R2N)2PCl......Page 377
Tris(dialkylamino)phosphonium salts, [(R2N)3PX]+Y-......Page 378
Phosphoramidates, (R1O)2P(O)NR22, and their thio analogs......Page 379
Hexaalkylphosphoric triamides, (R2N)3P(O), and hexaalkylthiophosphoric triamides, (R2N)3P(S)......Page 380
Miscellaneous compounds containing an N-P bond......Page 381
Miscellaneous compounds containing an N-As bond......Page 382
Dialkylaminosilanes, R2NSiX3......Page 383
Bis(dialkylamino)silanes, (R2N)2SiX2......Page 384
Dialkylaminoboranes, R2NBX2......Page 385
Miscellaneous compounds containing an N-B bond......Page 386
Compounds of alkaline-earth metals and zinc......Page 387
Compounds of first row transition metals......Page 388
Azo compounds......Page 389
N,N’-Azodioxides (nitroso dimers)......Page 390
Substances of the type RN=PNR’2......Page 391
Compounds containing an N=As bond......Page 392
Compounds Containing an N=Metal Bond......Page 393
References......Page 394
Biographical sketch......Page 400
2.08 Alkylphosphorus Compounds......Page 402
Primary phosphines from metallated phosphines......Page 403
Primary phosphines by addition of P-H to unsaturated compounds......Page 404
Primary phosphines by reduction of phosphonous and phosphonic compounds......Page 406
Dialkylphosphines......Page 407
Secondary phosphines from metallated phosphines......Page 408
Secondary phosphines by addition of P-H to unsaturated compounds......Page 409
Reduction of phosphinic and thiophosphinic compounds......Page 412
Reductive cleavage of P-C bonds......Page 413
Chiral secondary phosphines......Page 414
Tertiary phosphines from phosphines and alkylating agents......Page 415
Tertiary phosphines from electrophilic phosphorus and organometallic reagents......Page 416
Tertiary phosphines from metallated phosphines......Page 418
Addition to alkenes and alkynes......Page 420
Addition to other unsaturated compounds......Page 422
Tertiary phosphines by reduction......Page 423
Phosphinite method......Page 424
Kinetic resolution......Page 425
Alkylation/arylation of secondary phosphines......Page 426
Asymmetric transformation......Page 427
Quaternary alkylphosphonium salts from phosphines and alkylating agents......Page 428
Quaternary alkylphosphonium salts from phosphines, alcohol, and hydrogen halides......Page 429
Electrochemical synthesis of phosphonium salts......Page 430
Alkylphosphorus Compounds with a P-Cl Bond-RPCl2 and R2PCl......Page 431
Alkylphosphorus Compounds with a P-F, P-Br, and P-I Bond......Page 432
Alkylphosphinous Acid Derivatives-RPHOH, R2POH, etc.......Page 433
Alkylphosphonous Acid Derivatives-RP(OH)2, etc. Also Halides-RP(Hal)(OH), etc.......Page 435
Alkylphosphine Oxides-R3PO......Page 436
Alkylphosphinic Acid Derivatives-R2P(O)OH, etc. Also Halides-R2P(O)Hal, etc.......Page 440
Alkylphosphonic Acid Derivatives-RP(O)(OH)2, etc. Also Halides-RP(O)(Hal)OH, RP(O)(Hal)2, etc.......Page 443
Alkylthiophosphinous Acid Derivatives-R2PSH, etc.......Page 450
Alkylphosphine Sulfides-R3PS, etc.......Page 451
Alkylthiophosphonic Acid Derivatives-RP(S)(OH)2, RP(O)(SH)2, RP(S)(OH)(SH), etc.......Page 453
Alkylphosphorus Compounds with a P-Se and/or a P-Te Bond......Page 454
Amides of Alkylphosphinous Acid-R2PNR1......Page 455
Amides of Alkylphosphonous Acid-RP(NR1)2......Page 456
Amides of Alkylphosphonic Acid-RP(O)(NR12)2......Page 457
Other P-N Compounds......Page 458
Acyclic compounds......Page 459
Cyclic polyphosphines......Page 460
Alkylphosphorus Compounds with a P-Si Bond......Page 462
Alkylphosphorus Compounds with a P-Sn Bond......Page 463
Alkylphosphorus Compounds with a P-B Bond......Page 464
Alkylphosphorus Compounds with a P-M Bond......Page 465
Trialkylphosphoranes-R3PX2......Page 466
Monoalkylphosphoranes-RPX4......Page 467
References......Page 468
Biographical sketch......Page 479
2.09 Alkylarsenic, -antimony, and -bismuth Compounds......Page 482
Introduction......Page 484
Reaction of organometallics with alkylarsenic, -antimony, and -bismuth halides......Page 485
Arsonium ylides......Page 486
Pyrolysis of R3EX2 and R2EX3 (E=As, Sb)......Page 487
Miscellaneous methods......Page 488
Esters of alkylarsonous acids, R1As(OR2)2, and their analogous antimony and bismuth compounds......Page 489
Arsinolipids......Page 490
From R3SbX2 or R3Sb(OH)2......Page 491
R12EE’R2 (E=As, Sb, Bi; E’=S, Se, Te) from exchange reaction between tetraalkyldipnicogens and diorganodichalcoge......Page 492
Reaction of tertiary alkylarsine and -stibines with chalcogens......Page 493
Cleavage of As-N bonds......Page 494
From AsX3......Page 495
Miscellaneous methods......Page 496
From dialkylhaloarsines and -stibines......Page 497
From R2SbSiMe3......Page 498
With indium......Page 499
Cr and W complexes......Page 500
References......Page 501
Biographical sketch......Page 503
2.10 Alkylboron and -silicon Compounds......Page 504
Hydroboration of alkenes......Page 505
Dialkylboranes by hydroboration......Page 506
Trialkylboranes by hydroboration......Page 507
Organoboranes by equilibration (redistribution) and isomerization......Page 508
Organoboranes by alkylation alpha to boron......Page 509
Miscellaneous methods......Page 510
Hydroboration of alkenes......Page 511
Reaction of alcohols with a borane derivative......Page 513
Reaction of an organometallic reagent with a borane derivative......Page 514
Reaction of an organoborane with an aldehyde or ketone......Page 518
Miscellaneous methods......Page 519
Alkylaminoboranes and Related Compounds with a B-N Bond......Page 521
Alkylboranes with a B-Si Group......Page 522
Alkylboranes with Boron Having a Coordination Higher Than 3......Page 523
Hydridosilanes......Page 524
Tetraorganosilanes......Page 525
Alkylsilyl Halides......Page 527
Alkylsiloxanes......Page 529
Alkylsilazanes......Page 536
Compounds with Si-Si bonds......Page 537
Alkylsilicon Compounds with an Si-Metal Bond......Page 538
Alkylsilicon Compounds with Silicon Having a Coordination Higher Than 4......Page 539
References......Page 542
Biographical sketch......Page 549
2.11 Alkyl Metals......Page 550
From alkyl halides......Page 551
From other leaving groups......Page 552
Preparation by halogen-metal interconversion......Page 553
Preparation from other alkyl metals: transmetallation......Page 554
Addition to C-C double bonds: carbolithiation......Page 555
Preparation by oxidative addition: the Grignard reaction......Page 556
Carbomagnesation......Page 558
Other Derivatives......Page 559
M(III) derivatives......Page 560
M(IV) derivatives......Page 561
Alkylvanadium, -niobium, and -tantalum Derivatives......Page 562
Other derivatives......Page 563
Other derivatives......Page 564
M(III) and M(IV) derivatives......Page 565
M(II) derivatives......Page 566
M(III) derivatives......Page 567
Alkylcopper Derivatives......Page 568
Heterocuprates......Page 569
Alkylgold Derivatives......Page 570
Preparation by Transmetallation......Page 571
Mercuration......Page 572
Preparation by oxidative addition......Page 573
Alkylgallium and -indium Derivatives......Page 574
Preparation by oxidative addition......Page 575
References......Page 576
Biographical sketch......Page 579
2.12 Vinyl and Aryl Halides......Page 580
Vinyl halides by elimination reactions......Page 581
Vinyl halides from vinyl metallic species......Page 582
Vinyl halides from carbonyl compounds......Page 583
Vinyl halides by miscellaneous methods......Page 584
Aryl halides by electrophilic aromatic substitution......Page 585
Aryl halides by miscellaneous methods......Page 586
Vinyl fluorides from vinyl metallic species......Page 587
Vinyl fluorides by miscellaneous methods......Page 588
Aryl fluorides by electrophilic aromatic substitution......Page 590
Aryl fluorides by miscellaneous methods......Page 591
Vinyl chlorides from alkynes......Page 592
Vinyl chlorides from vinyl metallic species......Page 593
Aryl chlorides by electrophilic aromatic substitution......Page 594
Vinyl bromides by elimination reactions......Page 596
Vinyl bromides from alkynes......Page 597
Vinyl bromides by miscellaneous methods......Page 598
Aryl bromides by electrophilic aromatic substitution......Page 601
Vinyl iodides by elimination reactions......Page 602
Vinyl iodides from alkynes......Page 603
Vinyl iodides from vinyl metallic species......Page 604
Vinyl iodides from carbonyl compounds......Page 605
Vinyl iodides by miscellaneous methods......Page 606
Aryl iodides by electrophilic aromatic substitution......Page 607
Aryl iodides by miscellaneous methods......Page 608
References......Page 609
Biographical sketch......Page 613
Enols and Phenols: ROH......Page 614
Miscellaneous methods......Page 615
Fluorinated simple enols......Page 617
Sterically congested stable enols......Page 619
Aromatic nucleophilic substitution......Page 620
Oxidation of metallated arenes......Page 623
Claisen rearrangement......Page 624
The Fries rearrangement......Page 625
Ketoxime rearrangement......Page 626
Carbanion rearrangement......Page 627
Reduction of quinones......Page 628
Aromatization of cyclohexanones, cyclohexenones, and cyclohexadienones......Page 629
Annulation of acyclic fragments......Page 631
[4+2]-Annulation......Page 632
[4+2]-Cycloaddition......Page 633
[3+2+1]-Annulations......Page 635
[1+5]-Annulations......Page 636
O-Alkylation/acylation of enols, enolates, and other enol derivatives......Page 637
From alkynes......Page 639
From acetals......Page 641
By alkenylation of esters, lactones, and other carboxylic acid derivatives......Page 642
Homologation of alkenyl ethers and oxygenation of alkenyl electrophiles......Page 643
By olefin metathesis......Page 646
Aryl ethers......Page 647
Hypohalites (RO-Hal)......Page 650
Aryl peroxides......Page 651
Alkenyl and aryl sulfonates......Page 652
O-Alkenyl and O-aryl hydroxylamines......Page 654
O-Aryl- and O-alkenyloximes......Page 655
Alkenyl and aryl phosphites......Page 658
Alkenyl and aryl phosphates......Page 660
Metal and metalloid enolates......Page 661
Enolates of group 13 metals and metalloids......Page 662
Zinc......Page 665
Cobalt, Rhodium, and Palladium......Page 666
Metal and metalloid phenolates......Page 667
References......Page 670
Biographical sketch......Page 676
2.14 Vinyl and Aryl Chalcogenides: Sulfur-, Selenium-, and Tellurium-based Functional Groups......Page 678
Arenethiols from aryl halides......Page 679
The Herz reaction......Page 680
Arenethiols from arenesulfides......Page 681
Vinyl sulfides by enolization of thioic and dithioic esters......Page 682
Vinyl sulfides from alkynes......Page 683
Aryl sulfides from arenes......Page 684
Aryl sulfides from arenethiols......Page 685
Aryl sulfides from S-substituted arenethiols......Page 686
Aryl sulfides by reduction of sulfoxides and sulfones......Page 687
Miscellaneous methods......Page 688
Aryl sulfoxides......Page 689
Vinyl sulfones......Page 690
Aryl sulfones......Page 691
Vinyl and arenesulfonyl halides......Page 693
Arenesulfinic acids......Page 695
Arenesulfinates......Page 696
Aryl Di- and Polysulfides and Their Higher-coordinated Derivatives......Page 697
Aryl polysulfides......Page 698
Higher-coordinated derivatives of aryl disulfides......Page 699
Vinyl- and arenesulfenamides and derivatives......Page 700
Vinyl- and arenesulfinamides and derivatives......Page 702
Vinyl- and arenesulfonamides and derivatives......Page 703
Vinyl- and Arylsulfanylsilanes......Page 704
Areneselenols......Page 705
Vinyl selenides from alkynes......Page 706
Aryl selenides......Page 707
Aryl selenides from areneselenols......Page 708
Vinyl tellurides......Page 709
Aryl tellurides......Page 710
Areneselenyl halides......Page 711
Areneselenenic acids......Page 712
Functions Based on R1SeOR2 Units and Their Higher-coordinated Derivatives......Page 713
Aryl polyselenides......Page 714
RSeN Functions......Page 715
References......Page 716
Biographical sketch......Page 726
2.15 Vinyl- and Arylnitrogen Compounds......Page 728
From carbonyl compounds, acetals, ynamines, nitriles, and others......Page 729
Sulfonyl and sulfinyl enamines, enaminothiones, and beta-thioenamines......Page 735
Enaminones......Page 737
N-Acylenamines......Page 743
alpha- and beta-Cyanoenamines......Page 746
Miscellaneously substituted enamines......Page 747
From hydrides (RH)......Page 750
From nitro derivatives......Page 751
From azides......Page 754
Palladium-mediated methods......Page 755
Nickel-mediated methods......Page 762
Copper-mediated methods......Page 764
From phenols and derivatives......Page 767
From amines......Page 768
From carboxylic acids and derivatives......Page 769
From arylbismuth, aryllead, arylboron, aryltin, arylsilicon, and diaryliodonium reagents......Page 770
Salts of Enamines......Page 774
Hydroxylamines and Related Functions......Page 777
Hydroxylamines......Page 778
N-Oxides......Page 780
N,N-Bis-(silyloxy)enamines and N,N-Bis-(silyloxy)arylamines......Page 781
Sulfenamides......Page 783
Hydrazines......Page 784
Azoalkenes......Page 788
From oxidation of primary aromatic amines......Page 789
Other methods......Page 791
Azoxy Compounds......Page 792
From aromatic amines......Page 793
Systems Containing N,N,N, N,N,N,N, and N,N,N,N,N Functionalities......Page 794
alpha,beta-Unsaturated nitroso compounds......Page 798
Aromatic nitroso compounds......Page 799
Nitroalkenes......Page 801
beta-Nitroenamines......Page 807
Nitro-, di-, and polyenamines......Page 809
Aromatic electrophilic substitution......Page 810
Oxidation of primary arylamines and aromatic nitroso compounds......Page 816
Aryl Thionitroso Compounds......Page 818
Sulfoximines......Page 819
Aromatic sulfoximines......Page 820
Vinyl sulfurdiimides......Page 822
Aryl sulfurdiimides......Page 823
Sulfinamides......Page 825
Sulfamides......Page 827
Sulfonamides......Page 829
Aromatic Nitrosamines......Page 830
Aromatic Nitramines......Page 832
Aromatic diazonium salts......Page 833
N-P Functions......Page 836
N-As, N-Sb, or N-Bi Functions......Page 841
Compounds with a Boron-Nitrogen Bond......Page 842
Compounds with a Silicon-Nitrogen Bond......Page 844
Compounds with a Germanium-Nitrogen Bond......Page 847
N-Sn, N-Pb, N-Hg, and N-Al Bonds......Page 850
References......Page 853
Biographical sketch......Page 871
2.16 Vinyl- and Arylphosphorus Derivatives......Page 872
Reduction of arylphosphonous (ArP(OH)2) and arylphosphonic (ArP(O)(OH)2) acids and their derivatives with LiAlH4 (method A)......Page 873
Miscellaneous methods......Page 874
Hydrolysis (or alcoholysis) of metal phosphides (method C)......Page 875
Reaction of arylphosphinous (ArRPX), or arylphosphonous (ArPX2) halides, or phosphorus trihalides, or their ester derivatives with Grignard, organolithium, or organometallic reagents (method A)......Page 877
Copper-catalyzed reaction of diarylphosphines with aryl iodides (method C)......Page 878
Dialkoxytriorgano- and alkoxytetraorganophosphoranes......Page 879
Arylphosphonous Dihalides (Aryldihalophosphines) (ArPX2)......Page 881
Diarylphosphinous Halides (Diarylhalophosphines) (Ar2PX)......Page 883
Arylhalophosphoranes......Page 884
Arylphosphonous (ArP(OH)2) and Unsaturated Phosphonous Acids, and Their Derivatives......Page 885
Dialkyl phosphonates with Grignard reagents......Page 887
Phosphorus halides or esters with organometallic reagents......Page 888
Palladium-catalyzed reaction of alkenyl or aryl bromides with secondary phosphine oxides......Page 890
Arylphosphinic acid derivatives......Page 891
Hydrolysis of phosphonic halides, esters, amides, and aryltrichlorophosphonium salts (method A)......Page 893
Phosphonic acid derivatives......Page 894
Arylthiophosphinous Acids (Ar2PSH) and Their Derivatives......Page 899
Arylphosphine Sulfides (ArR1R2P=S)......Page 900
Arylthiophosphinic Acids and Their Derivatives (Ar2P(S)(OH), Ar2P(O)SH, Ar2P(S)SH, Ar2P(S)Hal)......Page 901
Arylthiophosphonic Acids and Their Derivatives (ArP(S)(OH)2, ArP(O)(OH)SH, ArP(O)(SH)2, ArP(S)OH(SH), ArP(S)(Hal)2)......Page 902
Compounds with a P-Se and/or a P-Te Bond......Page 904
Amides of Arylphosphinous Acid (Ar2PNR2, ArPHNR2)......Page 906
Amides of Arylphosphinic Acids (Ar2P(O)NR2, Ar2P(Se)NR2)......Page 907
Amides of Arylphosphonic Acids (ArP(O)(NR2)2, ArP(O)(NR2)Hal, ArP(S)(NR2)2, etc.)......Page 908
Y=S: Ar2P-N=S, Ar2P=N-S, etc.......Page 909
Y=P-: Ar2P-N=P, etc.......Page 910
Arylphosphorus Compounds with a P-P Bond......Page 911
Arylphosphorus Compounds with a P-As Bond......Page 912
Arylphosphorus Compounds with a P-Si Bond......Page 913
Arylphosphorus Compounds with a P-Sn Bond......Page 914
Hexavalent Phosphorus Compounds......Page 915
References......Page 917
Biographical sketch......Page 926
2.17 Vinyl- and Arylarsenic, -antimony, and -bismuth Compounds......Page 928
Transmetallation......Page 929
Halogen-metal exchange......Page 932
Reaction of organometallic reagents with arenes and alkynes......Page 933
Thermal processes: cycloaddition and thermal rearrangements......Page 934
Heteroaromatic Compounds of Arsenic, Antimony, and Bismuth......Page 935
Halogenation of Arsines, Stibines, and Bismuthines......Page 937
Displacement Reactions......Page 939
Preparation through Metal-Carbon Bond Formation......Page 940
Formation of Metal-Oxygen Bonds by Substitution Reactions......Page 941
Formation through Oxidative Processes......Page 944
Arsenic, Antimony, and Bismuth Compounds with the Heteroatom Bonded to Other Chalcogens......Page 945
Preparation of Organometal(III) Derivatives through Nucleophilic Displacement Reactions......Page 946
Preparation of Sulfur, Selenium, and Tellurium Derivatives by Oxidative Processes......Page 949
Preparation by Displacement of Halide and Halide Equivalents from the Metal......Page 950
Preparation by Formation of Metal-Nitrogen Bonds through Rearrangement Processes......Page 951
Organodiarsines, -distibines, and -dibismuthines......Page 952
Arsenic, Antimony, and Bismuth Compounds with the Heteroatom Bonded to a Metalloid......Page 953
Transition Metal Derivatives......Page 954
References......Page 955
Biographical sketch......Page 959
2.18 Vinyl- and Arylsilicon, germanium, and boron Compounds......Page 960
Uncatalyzed hydroboration......Page 961
Haloboration of alkynes......Page 963
Addition of B element bonds to C-C multiple bonds......Page 965
Metathesis of alkenylboronates......Page 968
From 1-alkynylboranes......Page 969
1,1-Organoboration......Page 970
Arylboranes from aryl metals......Page 971
Cross-coupling of boron compounds with aryl derivatives......Page 972
Borylation of arenes......Page 973
Hydrosilylation of alkynes......Page 974
Cyclization of dialkynes and alkenynes via hydrosilylation......Page 978
Bissilylation of alkynes......Page 980
Silylmetallation of alkynes......Page 981
Carbosilylation of alkynes......Page 983
Silylcarbonylation of alkynes......Page 984
Hydrometallatio of alkynylsilanes......Page 987
Intramolecular hydrosilylation of silylalkynes......Page 990
Other addition reactions......Page 992
Carbometallation of alkynylsilanes......Page 995
Intramolecular silylformylation......Page 997
Vinylsilanes from alkenyl metal and silicon reagents......Page 998
Alkenyl metals via halogen-metal exchange......Page 999
Alkenyl metals via hydrogen-metal exchange......Page 1000
Dehydrogenative silylation of alkenes with hydrosilanes......Page 1001
Silylative coupling (trans-silylation) and cross-metathesis of alkenes with vinylsilanes......Page 1002
Ring-closing metathesis (RCM) and ring-closing silylative coupling (RCSC) of silyldienes......Page 1006
Tandem ring-opening metathesis/cross-metathesis......Page 1007
Pd-catalyzed cross-coupling of vinylsilanes with organic halides......Page 1008
Other reactions of vinylsilanes......Page 1009
Vinylsilanes from allenes......Page 1010
Vinylsilanes from carbonyl compounds......Page 1011
Hydrosilylation of alkenynes and alkadiynes......Page 1013
Miscellaneous methods......Page 1014
Cumulenylsilanes......Page 1015
By silylation of aryl metals......Page 1016
By electrophilic and nucleophilic aromatic substitutions......Page 1018
By cycloaddition reactions......Page 1019
By transition metal-catalyzed coupling of aryl derivatives with silicon compounds......Page 1020
Miscellaneous reactions......Page 1022
Hydrogermylation......Page 1023
Other transition metal-catalyzed germylation processes......Page 1025
Addition of derivatives containing Ge=Ge or Ge=Si double bond to alkynes......Page 1026
Miscellaneous reactions......Page 1027
Arylgermanes......Page 1028
Miscellaneous reactions......Page 1029
References......Page 1030
Biographical sketch......Page 1041
Introduction and General Discussion......Page 1044
Metal-Halogen Exchange Reactions of Vinyl and Aryl Halides......Page 1045
Metallation of Arenes via Electrophilic Substitution......Page 1046
Metallation of Alkenes and Arenes via Deprotonation with Bases......Page 1047
Hydroalumination......Page 1050
Hydrosilations......Page 1051
Hydrostannations......Page 1054
Carbometallation with Organometals Containing Group 1 and 2 Metals......Page 1056
Carbosilanation, Gallation, and Zincation......Page 1057
Zirconium-catalyzed Carboalumination and Related Reactions......Page 1059
Carbocupration of Alkynes......Page 1060
Stoichiometric carbometallation with organotransition metals......Page 1061
Oxymetallation, Halometallation, and other Heterometallation Reactions......Page 1063
Oxidative Coupling-ring Expansion Tandem Processes......Page 1064
Oxidative 1,1-Bimetalloalkenes......Page 1065
Nonredox and Redox Transmetallation Reactions......Page 1067
Summary......Page 1070
References......Page 1073
Biographical sketch......Page 1076
Carbanions Adjacent to Halogen......Page 1078
Carbanions Adjacent to Chalcogen......Page 1079
Carbanions Adjacent to Nitrogen......Page 1080
Carbanions Adjacent to Metalloids......Page 1081
Carbocations Adjacent to Halogen......Page 1083
Carbocations Adjacent to Chalcogen......Page 1084
Carbocations Adjacent to Nitrogen......Page 1086
Stabilized Radicals Bearing One Heteroatom (R1R2C.X)......Page 1087
References......Page 1088
Biographical sketch......Page 1091
Alkynyl Halides......Page 1092
Chlorides......Page 1093
Bromides......Page 1096
The synthesis of alkynyl iodides......Page 1101
The synthesis of alkynyliodonium salts......Page 1108
Ynols and ynolates......Page 1110
Alkynyl ethers......Page 1112
Alkynyl esters......Page 1115
Alkynyl thioethers......Page 1116
Alkynyl sulfoxides and sulfones......Page 1121
Alkynyl selenides......Page 1124
Alkynyl tellurides......Page 1127
References......Page 1128
Biographical sketch......Page 1133
2.22 Alkynylnitrogen and -phosphorus Compounds......Page 1134
Primary and secondary ynamines......Page 1135
Functionalization of ynamines at the alkynyl position......Page 1136
From gamma-halogenoenamines......Page 1138
From trichloroenamines and dichloroenamines......Page 1140
From haloalkenes......Page 1141
Isomerization reactions......Page 1143
Miscellaneous methods......Page 1146
Nitroalkynes......Page 1148
Azoalkynes......Page 1149
Alkynyl isocyanates......Page 1150
N=X Functions......Page 1151
N-Si Functions......Page 1152
Ynamides......Page 1153
Secondary alkynylphosphines......Page 1159
From phosphorus trichloride......Page 1162
From phosphinous dichlorides......Page 1163
From chlorophosphines......Page 1164
Miscellaneous methods......Page 1165
From alkynyl halides......Page 1167
Quaternization of alkynylphosphines......Page 1168
Miscellaneous methods......Page 1169
Alkynyl phosphonites (X=OR)......Page 1170
Alkynylaminophosphines (X=NR)......Page 1171
Secondary alkynylhalogenophosphines......Page 1172
Secondary alkynylaminophosphines......Page 1173
Alkynylphosphine oxides......Page 1174
From chlorophosphine oxides......Page 1175
Other methods......Page 1176
Alkynylphosphine imides......Page 1177
From alkynyl organometallic reagents......Page 1178
Alkynylation of dialkyl phosphites......Page 1180
Elimination of alkenyl phosphonates......Page 1181
References......Page 1183
Biographical sketch......Page 1187
2.23 Alkynylarsenic, -antimony, -bismuth, -boron, -silicon, -germanium, and Metal Compounds......Page 1190
Method 4: Quaternization and related reactions......Page 1191
Method 1: Reaction of an antimony halide with a metal acetylide......Page 1192
Alkynylbismuth Compounds......Page 1193
Method 1: Reaction of a boron halide with a metal acetylide......Page 1194
Method 3: Reaction of an alkoxy-, thio-, or amino-dialkylborane with alkynyl metal reagents......Page 1195
Method 5: Reaction of an alkynyl metal with chloroaminoborane......Page 1196
Method 6: Reaction of an alkynyl metal with a borate, an alkynyl sodium with a chloroborate, and alkynyldialkoxyboranes from alkynyldiaminoboranes......Page 1197
Method 10: Reaction of alkynyl metals with trimethyl borate followed by fluoride-methoxy exchange......Page 1199
Method 1: The reaction of an organosilyl halide with an alkynyl metal derivative......Page 1200
Method 5: Desulfinylation of 2-trialkylsilyl vinyl sulfoxides......Page 1201
Method 1: Reaction of an organogermanium halide with a metal acetylide......Page 1202
Method 3: Modification of preformed alkynylgermanes......Page 1203
Alkynylcopper Compounds......Page 1204
Alkynyltin Compounds......Page 1205
References......Page 1206
Biographical sketch......Page 1209