Handbook of Heterocyclic Chemistry, Third Edition

Copyright......Page 1
Part 1 Preliminaries......Page 2
1.1 Foreword......Page 3
Survey of Possible Structures and Nomenclature......Page 4
Arrangement of Material in the Synthesis Chapters......Page 5
Explanation of the Reference System......Page 6
Structure of Heterocycles......Page 7
Arrangement of Structure Chapters......Page 8
Nomenclature......Page 9
Computer-Aided Studies of Heterocycles......Page 10
Oxygen and Sulfur Rings without Exocyclic Conjugation......Page 11
Ab Initio and DFT Calculations......Page 12
Glossary of General Terms Used in Chapters 2.2–2.5......Page 13
Structure of Six-membered Rings......Page 15
Fully-conjugated aromatic rings......Page 16
Rings without cyclic conjugation......Page 18
Fully-conjugated aromatic rings......Page 19
Rings without cyclic conjugation......Page 20
Rings Containing Nitrogen with Oxygen and/or Sulfur......Page 21
Rings Containing Nitrogen with Oxygen and/or Sulfur......Page 22
General Trends......Page 23
X-Ray Diffraction......Page 26
Aromatic rings......Page 27
Partially- and fully-saturated ring systems......Page 28
X-Ray Diffraction......Page 29
Chemical shifts......Page 32
Other ring systems......Page 37
Saturated systems......Page 40
UV Spectroscopy......Page 42
Ultraviolet and Related Spectra <1971PMH(3)67......Page 44
IR and Raman Spectra <1963PMH(2)161, 1971PMH(4)265......Page 46
Mass Spectrometry Substituent vibrations......Page 51
Background......Page 52
Melting and boiling points......Page 53
Structural criteria......Page 54
Background......Page 55
Conformations of Partially- and Fully-Reduced Rings......Page 56
N-Heterocyclic carbenes (NHCs)......Page 57
Prototropic tautomerism of rings without cyclic conjugation......Page 60
Prototropic Tautomerism of Rings......Page 61
Supramolecular Structures......Page 62
Structure of Five-Membered Rings with One Heteroatom......Page 65
Monocyclic systems......Page 66
Bicyclic systems......Page 67
Rings without cyclic conjugation......Page 68
Fully-conjugated rings......Page 69
Rings without cyclic conjugation......Page 70
General Trends......Page 71
General Trends......Page 74
Structure and energy......Page 76
X-Ray Diffraction......Page 77
Microwave Spectroscopy......Page 81
Parent aromatic compounds......Page 82
Substituted aromatic compounds......Page 83
1H NMR Spectroscopy......Page 86
Heteroatom NMR Spectroscopy......Page 89
UV Spectroscopy......Page 91
Ring vibrations......Page 94
Mass Spectrometry......Page 97
Substituted monocycles......Page 98
Benzo derivatives......Page 99
Saturated compounds......Page 100
Effect of substituents......Page 101
Benzo derivatives......Page 102
Azole rings containing carbonyl groups......Page 103
Gas–liquid chromatography......Page 104
Structural criteria......Page 105
Structural criteria......Page 106
Magnetic criteria......Page 109
Conformations of Partially- and Fully-Reduced Rings......Page 110
Conformations of Partially- and Fully-Reduced Rings......Page 111
2-Hydroxy derivatives......Page 112
Introduction......Page 113
Imidazoles......Page 114
Thiono-mercapto and amino-imino tautomerism......Page 115
Structure of Five-membered Rings with Two or More Heteroatoms......Page 117
Oxygen and Sulfur Rings with Exocyclic Conjugation......Page 122
Theoretical Methods......Page 123
Calculation of Molecular Properties......Page 127
Reactions and equilibria......Page 129
Structural Methods......Page 131
Microwave Spectroscopy......Page 135
Chemical shifts......Page 138
Coupling constants......Page 140
Nuclear Overhauser effects......Page 141
Low-temperature studies......Page 142
13C NMR Spectroscopy......Page 145
Nitrogen and Oxygen NMR Spectroscopy......Page 151
Parent compounds......Page 155
Photoelectron Spectroscopy......Page 164
Aromaticity of Fully-Conjugated Rings......Page 165
Energetic criteria......Page 169
Conformations of Heteroaryl Derivatives......Page 173
Annular tautomerism......Page 177
Tetrazoles......Page 179
Annular elementotropy......Page 180
3-Substituted derivatives......Page 181
2-Substituted derivatives......Page 182
4- and 5-Substituted derivatives......Page 183
Ring-Chain Tautomerism......Page 184
Valence Tautomerism......Page 185
Structure of Small and Large Rings......Page 188
With exocyclic conjugation......Page 189
Larger Rings......Page 191
Three- and Four-Membered Rings......Page 192
Seven- and Eight-Membered Rings......Page 194
Larger Rings......Page 195
X-Ray Diffraction......Page 196
Microwave Spectroscopy......Page 200
Three- and four-membered rings......Page 201
Seven or more ring atoms......Page 202
Electronic spectra of small-ring heterocyclic compounds......Page 203
Electronic spectra of large-ring heterocyclic compounds......Page 204
Mass Spectrometry......Page 205
Ring strain......Page 208
Small rings......Page 209
Large rings......Page 210
Pyramidal inversion at ring nitrogen......Page 211
Ring conformation......Page 212
Annular Tautomerism......Page 213
Valence Tautomerism......Page 214
Part 3: Reactivity of Heterocycles......Page 216
Heteroaromatic Reactivity......Page 217
Arrangement of the Reactivity Sections......Page 218
Reactivity of Six-membered Rings......Page 219
Pyridines......Page 222
Cationic rings......Page 223
Pyridones, N-oxides, and mesomeric betaines......Page 224
Fragmentation (22→23)......Page 225
Rearrangement to or elimination via Dewar heterobenzenes (24→25→26, 27→28)......Page 226
Rearrangement to or via heteroprismanes and heterobenzvalenes (30, 31)......Page 228
Rearrangement to or via 1,3-bridged heterocycles (33→34)......Page 229
Introduction......Page 230
Azines......Page 231
Effects of substituents on the basicity of pyridine......Page 232
Simple complexes......Page 233
N-Alkylation of pyridines......Page 234
Acyl halides and related compounds and Michael-type reactions......Page 235
Halogens......Page 236
Peracids......Page 237
Species undergoing reaction and the reaction mechanism......Page 238
Reactivity and effect of substituents......Page 239
Pyridines......Page 240
Azine N-oxides......Page 241
Acid-catalyzed hydrogen exchange......Page 242
Pyridines......Page 243
Azines......Page 244
Pyridones, pyrones, azinones, and N-oxides......Page 245
Acylation and alkylation......Page 0
Kolbe and Reimer–Tiemann reactions......Page 247
Oxidation......Page 248
Pyridines......Page 249
Pyridones and azinones......Page 250
Other azines......Page 251
Alkylpyridinium cations......Page 253
Other pyridinium ions......Page 254
Other cationic rings......Page 255
Pyridones, pyrones, azinones, etc......Page 256
Pyridines and azines......Page 257
Other cationic rings......Page 260
Phosphorus nucleophiles......Page 261
Organometallic compounds......Page 262
Activated methyl and methylene carbanions......Page 267
Cyanide ions......Page 269
Pyridines......Page 271
Azines......Page 272
Cationic rings......Page 273
Attack by Bases at Hydrogen Attached to Ring Carbon or Ring Nitrogen......Page 274
Metallation at a ring carbon atom (see also Sections 3.2.3.10.2.2–3.2.3.10.2.5 and 3.2.3.11.1)......Page 275
Hydrogen exchange at ring carbon in azinium cations......Page 277
Proton loss from a ring nitrogen atom......Page 278
Alkyl and α-hydroxyalkyl radicals......Page 279
Neutral species: Reactions with metals......Page 281
Catalytic hydrogenation (see also Section 3.2.1.6.9)......Page 282
Heterocyclic systems with one heteroatom......Page 283
Diazines......Page 284
Triazines......Page 285
Heterocycles as inner dienes in [1+4] cycloadditions......Page 286
Inner 1,3-dipoles......Page 288
Heterocycles as dienophiles......Page 289
Heterocycles as 4π-components in [4+4] cycloaddition......Page 290
By reaction at sulfur......Page 291
Reactions with nucleophiles......Page 292
Thiabenzenes and Related Compounds......Page 293
Annular tautomerism......Page 294
By loss of attached leaving groups with bonding electrons......Page 295
By oxidation or dehydrogenation......Page 296
Electrocyclic ring opening (valence tautomerism)......Page 298
Electrophilic substitution......Page 299
Cycloaddition reactions......Page 300
Other reactions......Page 302
Tautomeric equilibria......Page 303
Ring fission......Page 304
Stereochemistry......Page 305
Pyridines and azines......Page 306
Reactions of substituents not directly attached to the heterocyclic ring......Page 308
Electrophilic substitution of benzopyridones and related compounds......Page 309
Nucleophilic attack......Page 310
Electrophilic substitution......Page 311
Hydroxy groups......Page 312
Alkyl groups: Reactions via proton loss......Page 313
Alkylazines: Reactions involving traces of reactive anions or traces of methylene enamines......Page 314
Formation of stable anhydro-bases......Page 316
Anhydro-bases as intermediates......Page 317
Electrophilic substitution......Page 318
Decarboxylation of carboxy groups directly attached to ring......Page 319
Nucleophilic displacement of cyano groups......Page 320
Examples of normal reactivity......Page 321
Orientation of reactions of aminopyridines and -azines with electrophiles......Page 322
Reaction of aminoazines with electrophiles at the amino group......Page 323
Nucleophilic displacement......Page 324
Intramolecular reactions of amino group producing rings......Page 325
Nitro groups......Page 326
Azides......Page 327
Hydroxy groups and hydroxy–oxo tautomeric equilibria......Page 328
Pyridones, pyrones, thiinones, azinones, etc.: General pattern of reactivity......Page 329
Pyridones, pyrones, and azinones: Electrophilic attack at carbonyl oxygen......Page 330
Pyridones, pyrones, and azinones: Nucleophilic displacement of carbonyl oxygen......Page 331
Alkoxy and aryloxy groups......Page 333
Acyloxy groups......Page 335
Thiones......Page 336
Replacement of halogen by hydrogen or a metal (including transmetallation) or by coupling......Page 337
The SRN mechanistic pathway......Page 339
Reactivity dependence on halogen and nucleophile......Page 340
Reactivity in polyhalo compounds......Page 342
Organometallic nucleophiles......Page 344
Suzuki–Miyaura reactions......Page 345
Stille reactions......Page 347
Sonogashira reactions......Page 348
Heck reactions......Page 349
Amination, alkoxylation, and alkthiolation reactions......Page 350
Overall survey of reactivity......Page 352
Proton loss from a carbon atom......Page 353
N-Acyl and related groups......Page 354
Prototropic equilibria......Page 355
Other reactions of N-amino compounds......Page 356
Rearrangement reactions......Page 357
Substituents Attached to Ring Sulfur Atoms......Page 359
Reactivity of Five-Membered Rings with One Heteroatom......Page 360
General Survey of Reactivity......Page 362
Thermal and Photochemical Reactions Involving No Other Species......Page 363
Pyrrole Grignard reagents......Page 365
Other pyrrole anion nucleophiles......Page 366
N-Arylation......Page 368
N-Vinylation......Page 369
Oxidation......Page 370
Relative reactivities of heterocycles......Page 371
Directing effects of the ring heteroatom......Page 372
Directing effects of substituents in monocyclic compounds......Page 373
Range of substitution reactions......Page 374
Base strengths......Page 375
Nitration......Page 376
Sulfonation......Page 377
Halogenation......Page 378
Pyrroles......Page 380
Thiophenes......Page 383
Alkylation (see also Section 3.3.3.8.8)......Page 385
Formation of carbinols or carbonium ions......Page 389
Further reactions of carbonium ions......Page 390
Mannich reaction......Page 391
Diazo coupling......Page 393
Electrophilic oxidation......Page 394
Deprotonation at carbon......Page 397
Reactions of cationic species with nucleophiles......Page 398
Vicarious nucleophilic substitution and related reactions......Page 399
Carbenes and nitrenes......Page 401
Radical attack......Page 403
Reactions with free electrons......Page 406
Heterocycles as inner ring dienes......Page 407
Five-membered heterocycles as dienophiles......Page 411
[2+2] Cycloaddition reactions......Page 412
Other cycloaddition reactions......Page 413
Thiophene Sulfones and Sulfoxides (see also Section 3.3.1.3.2.3)......Page 414
Aromatization of dihydro compounds......Page 416
Other reactions......Page 417
Tetrahydro Derivatives......Page 418
Survey of structures......Page 419
Reactions of hydroxy compounds with electrophiles......Page 420
Reactions of anions with electrophiles......Page 421
Carbonyl not adjacent to heteroatom......Page 422
Nucleophilic substitution of substituents......Page 423
Electrophilic attack......Page 424
Reactions with electrons – reduction reactions......Page 425
Vinyl groups......Page 426
Substituted alkyl groups: General......Page 428
Hydroxymethyl......Page 430
Aminomethyl......Page 431
Carboxylic acids, esters, and anhydrides......Page 432
Acyl groups......Page 433
Nitro......Page 434
Amino......Page 435
S-Linked Substituents......Page 436
Reductive dehalogenation......Page 437
General......Page 438
Formation of C–C bonds......Page 439
Formation of C–S bonds......Page 441
Ring-opening reactions......Page 442
Transition metal-catalyzed cross-coupling reactions......Page 443
Mercury derivatives......Page 447
Substituents Attached to the Pyrrole Nitrogen Atom......Page 448
Substituents Attached to the Thiophene Sulfur Atom......Page 449
Reactivity of Five-membered Rings with Two or More Heteroatoms......Page 450
Reactivity of neutral azoles......Page 453
Azole anions......Page 454
N-Oxides, N-imides, N-ylides of azoles......Page 455
Thermal fragmentation......Page 456
Photochemical fragmentation......Page 459
Equilibria with open-chain compounds......Page 460
Rearrangement to other heterocyclic species......Page 461
Reaction sequence......Page 463
Effect of azole ring structure and of substituents......Page 464
Proton acids on neutral azoles: Basicity of azoles......Page 465
N-Hydrogen acidity of azoles......Page 466
Basicity and acidity in gas phase......Page 467
Chelate complexes......Page 468
Alkyl halides and related compounds: Azoles without a free NH group......Page 469
Alkyl halides and related compounds: Compounds with a free NH group......Page 471
Acyl halides and related compounds......Page 475
Peracids......Page 476
Aminating agents......Page 477
Ease of reaction......Page 478
Effect of substituents......Page 479
Nitration......Page 480
Halogenation......Page 481
Acylation, formylation, and alkylation......Page 483
Diazo coupling......Page 484
Reactions with aldehydes and ketones......Page 485
Oxidation......Page 486
Electrophilic attack......Page 487
Nucleophilic attack......Page 488
Nucleophilic Attack at Carbon......Page 489
Neutral azoles......Page 490
Azolium ions......Page 491
Azoles......Page 493
Azolium ions......Page 494
Halide ions......Page 496
Organometallic compounds......Page 497
Activated methyl and methylene carbanions......Page 498
Reduction by complex hydrides......Page 499
Base Attack at Hydrogen Attached to Ring Carbon or Ring Nitrogen......Page 501
Metallation at a ring carbon atom......Page 502
Hydrogen exchange at ring carbon in neutral azoles......Page 504
Hydrogen exchange at ring carbon in azolium ions and dimerization......Page 505
C-Substitution via electrophilic attack at N, deprotonation, and rearrangement......Page 506
Ring cleavage via C-deprotonation......Page 507
Carbenes and nitrenes......Page 509
Thiation......Page 510
Electrochemical reactions and reactions with free electrons......Page 511
Other reactions at surfaces (catalytic hydrogenation and reduction by dissolving metals)......Page 512
Heterocycles as inner ring dienes......Page 514
Heterocyclic derivatives as outer ring dienes......Page 518
Heterocycles as dienophiles......Page 519
[2+2] Cycloaddition reactions......Page 520
Compounds not in tautomeric equilibrium with aromatic derivatives......Page 521
Aromatization......Page 523
Ring contraction......Page 525
Other reactions......Page 526
Ring fission......Page 530
Other reactions......Page 531
Substituent environment......Page 532
The effect of one substituent on the reactivity of another......Page 533
Reactions of substituents involving ring transformations......Page 534
Oxidative degradation......Page 536
Nucleophilic attack......Page 537
Rearrangements......Page 538
Reactions similar to those of toluene......Page 539
Alkylazoles: Reactions involving essentially complete anion formation......Page 540
Reactions of alkylazoles involving traces of reactive anions......Page 541
C-Alkyl-azoliums, -dithiolyliums, etc.......Page 542
Aryl groups: Other reactions......Page 544
Carboxylic acids......Page 545
Aldehydes and ketones......Page 546
Ring fission......Page 547
Dimroth rearrangements......Page 548
Reactions with electrophiles (except nitrous acid)......Page 549
Diazo anhydrides......Page 550
Diazonium salts......Page 551
Oxidation of aminoazoles......Page 552
Azidoazoles......Page 553
Tautomeric forms: Interconversion and modes of reaction......Page 554
Nucleophilic displacement......Page 555
4- and 5-Hydroxyazoles with heteroatoms-1,3 and 4-hydroxyazoles with heteroatoms-1,2......Page 556
Alkoxy and aryloxy groups......Page 557
Thiones......Page 558
Alkylthio groups......Page 559
Nucleophilic displacements: Neutral azoles......Page 560
Nucleophilic displacements: Haloazoliums......Page 563
Other reactions......Page 564
Reactions of organometallic nucleophiles......Page 565
Transition metal-catalyzed cross-coupling reactions......Page 566
Aryl groups......Page 569
Alkyl and alkenyl groups......Page 571
Acyl and carboxy groups......Page 575
N-Amino groups......Page 577
N-Nitro groups......Page 578
N-Hydroxy groups and N-oxides......Page 579
N-Silicon, phosphorus, sulfur, and related groups......Page 580
General Survey......Page 582
Radicals......Page 583
Fragmentation Reactions......Page 584
Rearrangements......Page 586
Protonation......Page 589
Alkylation, Arylation, and Acylation......Page 591
Nucleophilic Attack on Ring Heteroatoms......Page 593
Reactions of Three-Membered Rings......Page 595
Reactions of Four-Membered Rings......Page 600
Reactions of Carbonyl Derivatives of Four-Membered Rings......Page 601
Large Rings......Page 602
Base Attack on Protons Attached to Ring Atoms......Page 603
Reactions with Radicals and Carbenes......Page 605
Oxidation......Page 607
Reduction (see also Section 3.5.5)......Page 608
Heterocycles as dienes......Page 609
1,3-Dipolar Cycloadditions......Page 611
Reactivity of Transition Metal Complexes......Page 613
C-Linked Substituents......Page 614
N- and S-Linked Substituents......Page 616
Part 4: Synthesis of Heterocycles......Page 617
Aims and Organization......Page 618
Ring Formation via Cycloaddition......Page 619
1,3-Dipolar cycloadditions......Page 620
Ring Closure of a Single Component......Page 622
Electrocyclic Reactions......Page 624
Ring Atom Interchange......Page 625
Ring Expansions......Page 626
Ring Closure with Simultaneous Ring Opening......Page 627
Synthesis of Monocyclic Rings with One Heteroatom......Page 628
Oxiranes......Page 629
Aziridines......Page 631
Thiiranes......Page 632
Four-membered rings......Page 633
Five-membered rings......Page 634
Oxiranes......Page 635
Aziridines......Page 636
Four-membered rings......Page 637
Five-membered rings......Page 639
Six-membered rings......Page 640
Larger rings......Page 641
From Acyclic Compounds by Formation of One C-C Bond......Page 642
From Carbocyclic Compounds......Page 643
Reactions involving ring expansion......Page 644
Reactions without change in ring size......Page 645
Ring contraction......Page 646
From Acyclic Compounds by Concerted Formation of Two Bonds......Page 647
Z Atom component acting as nucleophile......Page 649
From Acyclic Compounds by Ring-Closing Metathesis......Page 650
From Heterocycles......Page 651
Overview......Page 652
From C4Z or C4 units......Page 653
From C3ZC or C3 and CZ units......Page 658
From C2 and ZCC units......Page 659
From C2 and CZC units......Page 662
From C5 units......Page 664
With C-C bond formation......Page 665
With ring expansion......Page 667
No change in ring size......Page 669
With ring contraction......Page 670
Synthesis of Seven- and Eight-Membered Rings......Page 672
Other methods......Page 674
From other six-membered rings......Page 677
Synthesis of Seven-Membered and Larger Rings......Page 678
Synthesis of Monocyclic Rings with Two or More Heteroatoms......Page 680
Substituent Introduction and Modification in Azines......Page 682
Three-membered Rings......Page 683
1,2-Diazetidines......Page 684
1,2-Oxazetidines......Page 686
1,2-Thiazetidines......Page 687
1,2-Dioxetanes......Page 688
1,2-Dithietanes......Page 689
Pyrazoles and isoxazoles from 1,3-diketones......Page 690
Synthesis by Z–Z bond formation......Page 692
Other methods from acyclic precursors......Page 694
From other heterocycles......Page 696
Synthesis from hydrazine or hydroxylamine derivatives......Page 698
By cycloaddition reactions......Page 700
Other methods from acyclic precursors......Page 702
From other heterocycles......Page 703
1,2-Diazepines......Page 704
1,2-Dioxepans and 1,2-dithiepans......Page 707
1,3-Diazetidines......Page 708
1,3-Thiazetidines......Page 709
1,3-Dithietanes......Page 710
Synthesis from C2+ZCZ′ components......Page 711
Synthesis of imidazoles, oxazoles, and thiazoles from acylamino ketones......Page 713
Other syntheses of imidazoles, oxazoles, thiazoles, dithiolyliums, and oxathiolyliums by cyclization of C2ZCZ′ components......Page 714
Synthesis of azolinones and reduced rings from acyclic precursors......Page 717
Synthesis from other heterocycles......Page 721
C3+ZCZ-type cyclizations......Page 723
ZC3Z+C (5+1) and (6+0) cyclizations......Page 725
[4+2] Cyclizations......Page 726
Syntheses from other heterocycles......Page 728
1,3-Diazepines......Page 730
1,3-Oxazepines and 1,3-thiazepines......Page 731
1,3-Dioxepins and 1,3-dithiepins......Page 733
Pyrazines from acyclic compounds......Page 734
1,4-Dioxins, 1,4-dithiins, 1,4-oxazines, and 1,4-thiazines......Page 736
From heterocyclic precursors......Page 738
1,4-Diazepines......Page 741
1,4-Oxazepines and 1,4-thiazepines......Page 742
1,4-Dioxepins and 1,4-dithiepins......Page 744
Three- and Four-membered Rings......Page 745
1,2,3-Triazoles and 1,2,3-thiadiazoles......Page 746
1,2,5-Oxadiazoles......Page 747
1,2,5-Thiadiazoles......Page 748
1,2,3-Triazoles by dipolar cycloadditions......Page 749
Six-membered Rings......Page 750
From acyclic intermediates containing the preformed Z–Z′ bond......Page 751
From acyclic intermediates by formation of the Z–Z′ bond......Page 754
From other five-membered heterocycles......Page 755
By ring contraction......Page 757
1,2,4- Triazines......Page 758
Rings containing O or S atoms......Page 759
Heteroatoms in the 1,2,4-positions......Page 761
Seven-membered rings with heteroatoms in the 1,2,5-positions......Page 763
s-Triazines......Page 764
Compounds Containing O or S Atoms......Page 765
Seven-membered Rings......Page 767
Five-membered Rings......Page 768
Six-membered Rings......Page 771
Synthesis of Bicyclic Ring Systems Without Ring Junction Heteroatoms......Page 773
Synthesis by Substituent Introduction and Modification......Page 774
Four-membered rings......Page 775
Ring closure by formation of Z-C(2) bond......Page 777
The Fischer indole synthesis......Page 782
Benzofurans......Page 783
Gassman synthesis of indoles and benzo[b]furans......Page 784
Indole synthesis by intramolecular Heck reaction......Page 785
Oxindoles......Page 786
Photochemically mediated cyclizations......Page 787
C(3) as nucleophile......Page 788
Transition metal-catalyzed cyclizations......Page 789
From other heterocycles......Page 790
From or via o-substituted cinnamoyl derivatives......Page 791
Formation of a C–C bond by reaction of a multiple bond with a benzene ring......Page 792
Quinolones, benzopyrones, and benzothiinones......Page 793
Quinolines......Page 794
Partially-saturated rings......Page 795
Synthesis via cycloaddition reactions......Page 796
Synthesis from other heterocycles......Page 797
Seven-Membered and Larger Rings......Page 798
Five-Membered Rings: Isoindoles and Related Compounds......Page 799
Overview of ring syntheses of isoquinolines, benzo[c]pyrans, and their derivatives......Page 801
Ring closure of an o-disubstituted benzene......Page 802
From a β-phenethylamine......Page 803
From a benzylimine......Page 804
Four-Membered Rings......Page 805
Indazoles......Page 806
Anthranils, benzisothiazoles, and saccharins......Page 807
Cinnolines......Page 808
Rings containing O or S atoms......Page 810
Seven-Membered Rings......Page 811
Ring closure of an o-disubstituted benzene or hetarene......Page 812
Quinazolines and azinopyrimidines by cyclization procedures......Page 814
Rings containing O or S atoms......Page 816
From other heterocycles......Page 817
Seven-membered rings with heteroatoms 1,3 to a ring junction......Page 818
Seven-membered rings with heteroatoms 2,4 to a ring junction......Page 820
Quinoxalines and Azinopyrazines......Page 821
1,4-Benzoxazines and 1,4-Benzothiazines......Page 822
Rings Containing Oxygen and/or Sulfur Atoms......Page 824
1,4-Benzodiazepines......Page 825
1,4- and 4,1-Benzoxazepines, 1,4- and 1,5-benzothiazepines, and 1,4-benzodioxepins......Page 826
Seven-Membered Rings with Two Heteroatoms 1,5 to a Ring Junction......Page 829
Six-Membered Rings......Page 830
Seven-Membered Rings......Page 832
Five-Membered Heterocyclic Rings......Page 834
Three heteroatoms in the 1,2,3-positions......Page 835
1,2,4-Benzotriazines......Page 837
Six-membered rings containing O or S atoms......Page 839
Four heteroatoms......Page 840
Heteroatoms 1,2,4 to a ring junction......Page 841
Heteroatoms 1,2,5 to a ring junction......Page 842
Heteroatoms 1,3,4 to a ring junction......Page 843
Heteroatoms 1,3,5 to a ring junction......Page 845
Four or more heteroatoms......Page 846
Overview of synthetic methods for carbazoles, dibenzofurans, and dibenzothiophenes......Page 848
Formation of C–C bond......Page 849
Formation of C–Z bond......Page 851
Miscellaneous methods......Page 852
Six-membered Rings......Page 853
Two Adjacent Fused Rings, Two Heteroatoms......Page 854
Two Nonadjacent Fused Rings, One Heteroatom......Page 856
Phenoxazines and Phenothiazines......Page 858
Dibenzodiazepins, Dibenzoxepins, and Dibenzothiepins......Page 860
peri-Annulated Heterocyclic Systems......Page 862
Three Fused Rings......Page 863
Synthesis of Fused Ring Systems with Ring Junction Heteroatoms......Page 865
Formation of Three- or Four-Membered Rings with One N Atom at a Ring Junction......Page 866
[5–5] Systems......Page 867
[5–6] Systems......Page 868
Pyrazolo-fused systems......Page 870
Imidazo-fused systems......Page 871
Thiazolo-fused systems......Page 873
Oxazolo- and isoxazolo-fused systems......Page 875
1,2,4-Triazolo[b]-, 1,2,4-thiadiazolo[b]-, and 1,3,4-thiadiazolo[b]-fused systems......Page 876
1,2,4-Triazolo[c]- and 1,2,4-thiadiazolo[c]-fused systems......Page 879
Three Other Heteroatoms: Fused Tetrazoles......Page 880
Ring Formation Using a Three-Atom Fragment......Page 881
Ring Formation Using a Two-Atom Fragment......Page 883
Ring Formation Using a One-Atom Fragment......Page 884
Cycloaddition and Ring Transformation Reactions......Page 885
Formation of a Seven-Membered Ring with One N Atom at a Ring Junction......Page 887
Five-Membered Rings......Page 888
Six-Membered Rings......Page 890
Sulfur at a Ring Junction......Page 891
References......Page 893
Index......Page 947
Journal Abbreviations......Page 981