Denitrogenative Transformation of Nitrogen Heterocycles explores all 10 polynitrogen heterocycles that are known to undergo denitrogenative transformations to date. Following highlights on the remarkable modifications encountered in the synthesis of nitrogen heterocycles, the chapters use a reaction-based approach to explain denitrogenative transformations in detail.
This book covers the exponential growth in scientific literature in the last few decades for denitrogenative reactions of polynitrogen heterocycles which play a key role in natural products, medicinal chemistry, pharmaceuticals, biochemistry, and material sciences. This book also discusses denitrogenative cascade reactions, which accomplish powerful transformations from simple polynitrogen heterocycles to more complex molecules in modern synthetic chemistry.
Written by a highly qualified academic with significant experience in the field, Denitrogenative Transformation of Nitrogen Heterocycles covers sample topics including: - Transannulation of N-sulfonyl-1,2,3-triazoles with polar multiple bonds such as carbonyls and nitriles and non-polar multiple bonds such as alkenes, alkynes, and allenes- Insertion of azavinyl carbenes to C-X/X-X bond, denitrogenative rearrangements of N-sulfonyl-1,2,3-triazoles, and denitrogenative transformations of NH- and N-fluoroalkyl-1,2,3-triazoles- Metal-catalyzed and metal-free denitrogenative transformations of pyridotriazoles and denitrogenative transannulation of benzotriazoles and thiadiazoles- Denitrogenative transformations of tetrazoles and radical denitrogenative transformations of polynitrogen heterocycles
The first book of its kind on the subject, Denitrogenative Transformation of Nitrogen Heterocycles is an essential reference for researchers and scientists working in organic chemistry, organometallic chemistry, and transition metal catalysis, as well as academics and industry professionals in related fields.
Table of Contents
Preface xvii
1 Synthesis of Diverse Nitrogen Heterocycles Explored in Denitrogenative Transformations 1
Monalisa Akter and Pazhamalai Anbarasan
1.1 Introduction 1
1.2 Synthesis of 1,2,3-Triazoles 1
1.2.1 Synthesis of NH-Triazoles 1
1.2.2 Synthesis of N-Sulfonyl-1,2,3-triazoles 6
1.2.3 Synthesis of N-Trifluoromethyl-1,2,3-triazoles 8
1.2.4 Synthesis of 5-Iodo-1,2,3-triazoles 10
1.2.5 Synthesis of Pyridotriazoles 11
1.2.6 Synthesis of Triazoloindoles 12
1.2.7 Synthesis of Benzotriazoles 12
1.3 Synthesis of 1,2,3-Thiadiazoles 13
1.4 Synthesis of Tetrazoles 13
1.4.1 Synthesis of 1H-Tetrazoles 13
1.4.2 Synthesis of Pyridotetrazoles 15
1.4.3 Synthesis of Tetrazolo[1,5-a]quinolines 16
1.5 Synthesis of 3-Aminoindazoles 17
1.6 Synthesis of Benzotriazinones 18
1.7 Summary and Outlook 20
References 20
2 Transannulation of N-Sulfonyl-1,2,3-triazoles with Polar Multiple Bonds 31
Chuan-Ying Li and Ze-Feng Xu
2.1 Introduction 31
2.2 Reaction of N-Sulfonyl-1,2,3-triazoles with Carbonyls 31
2.3 Reaction of N-Sulfonyl-1,2,3-triazoles with Nitriles 42
2.4 Reaction of N-Sulfonyl-1,2,3-triazoles with Polar Multiple Bonds Beyond Carbonyls and Nitriles 44
2.5 Conclusion 47
References 47
3 Transannulation of N-Sulfonyl-1,2,3-triazoles with Nonpolar Multiple Bonds such as Alkenes, Alkynes, and Allenes 51
Prasiddha Nagarajan, Akhil Rampally, and Sudam G. Dawande
3.1 Introduction 51
3.2 Transannulation of N-Sulfonyl-1,2,3-triazoles with Alkenes 52
3.2.1 Intermolecular Transannulation with Alkenes 52
3.2.2 Intramolecular Transannulation with Alkenes 63
3.3 Transannulation of N-Sulfonyl-1,2,3-triazoles with 1,3-Dienes 64
3.3.1 Intermolecular Transannulation with 1,3-Dienes 65
3.3.2 Intramolecular Transannulation with 1,3-Dienes 68
3.4 Transannulation of N-Sulfonyl-1,2,3-triazoles with Alkynes 69
3.4.1 Intermolecular Transannulation with Alkynes 69
3.4.2 Intramolecular Transannulation with Alkynes 73
3.5 Transannulation of N-Sulfonyl-1,2,3-triazoles with Allenes 75
3.5.1 Intermolecular Transannulation with Allenes 75
3.5.2 Intramolecular Transannulation with Allenes 78
3.6 Summary and Outlook 79
References 80
4 Transannulations of N-Sulfonyl-1,2,3-triazoles with Carbo/Heterocycles 83
Mikhail S. Novikov and Nikolai V. Rostovskii
4.1 Introduction 83
4.2 Transannulations with Ring Retention 85
4.2.1 Aromatic and Heteroaromatic Rings 85
4.2.2 Nonaromatic Rings 89
4.3 Transannulations with Ring Opening 90
4.3.1 Heteroaromatic Rings 90
4.3.2 Nonaromatic Rings 101
4.4 Summary and Outlook 110
References 111
5 Insertion of Azavinyl Carbenes to C - H/X - H Bond 115
Yury N. Kotovshchikov and Gennadij V. Latyshev
5.1 Abbreviations 115
5.2 Introduction 116
5.3 Insertion Reactions of N1-Sulfonyl-1,2,3-triazoles 116
5.3.1 C - H Insertion 116
5.3.2 O - H Insertion 133
5.3.3 N - H Insertion 149
5.3.4 B - H Insertion 154
5.3.5 Si - H and P - H Insertion 155
5.4 Insertion Reactions of 5-Iodo-1,2,3-triazoles 156
5.5 Summary and Outlook 160
Acknowledgment 160
References 160
6 Insertion of Azavinyl Carbenes to C - X/X - X Bond 171
Claire Empel and Rene M. Koenigs
6.1 Introduction 171
6.2 1,3-Difunctionalization 172
6.3 [2,3]-Sigmatropic Rearrangement Reactions 180
6.4 Insertion into X - X bonds 184
6.5 Conclusion 184
References 184
7 Denitrogenative Rearrangements of N-Sulfonyl-1,2,3-triazoles 189
Om Prakash Dash, Shivam Pandey, and Chandra M. R. Volla
7.1 Introduction to Carbenes 189
7.2 Metal Carbenoids 189
7.3 Metal Carbenoids Derived from Diazo Compounds 191
7.4 α-Imino Metal Carbenoids and Their Reactivity 191
7.5 Denitrogenative Rearrangements of N-Sulfonyl-1,2,3-triazoles Through Azadiene Formation 193
7.6 Denitrogenative Rearrangements of N-Sulfonyl-1,2,3-triazoles Through Zwitterionic Intermediate 200
7.7 Denitrogenative Rearrangements of N-Sulfonyl-1,2,3-triazoles Through Ylide Formation 201
7.8 Denitrogenative Rearrangements of N-Sulfonyl-1,2,3-triazoles Through Ketenimine Formation 206
7.9 Conclusion 207
Acknowledgments 208
References 208
8 Denitrogenative Transformations of NH- and N-Fluoroalkyl-1,2,3-triazoles211
Vladimir Motornov and Petr Beier
8.1 Introduction 211
8.2 Denitrogenation of NH-1,2,3-Triazoles 211
8.3 Denitrogenation of N-Fluoroalkyl-1,2,3-triazoles 218
8.4 Summary and Outlook 223
Acknowledgments 223
References 223
9 Asymmetric Perspective on Denitrogenative Transformation of 1,2,3-Triazoles 227
Pokhriyal Yamini, Akanksha Babbar, and Dongari Yadagiri
9.1 Introduction 227
9.2 Rhodium-Catalyzed Cyclopropanation Reactions 227
9.3 Rhodium-Catalyzed C - H Insertion Reactions 233
9.4 Rhodium-Catalyzed Transannulation Reactions 236
9.5 Miscellaneous Reactions 240
9.5.1 Relay Catalysis 240
9.5.2 Atom Transfer Reactions 242
9.6 Application in Natural Product and Total Synthesis 243
9.7 Summary and Outlook 246
Acknowledgments 246
References 246
10 Denitrogenative Transformations of 3-Diazoindolin-2-imines 251
Kavuri Rupa and Pazhamalai Anbarasan
10.1 Introduction 251
10.2 Synthesis of 3-Diazoindolin-2-imines 251
10.3 Insertion Reactions of 3-Diazoindolin-2-imines 253
10.3.1 Insertion into X - H Bonds 253
10.3.2 Insertion into C - H Bonds 255
10.3.3 Insertion into C - X Bonds 257
10.4 Annulation Reactions of 3-Diazoindolin-2-imines 260
10.5 Miscellaneous Reactions 271
10.6 Summary and Outlook 277
References 277
11 Metal-Catalyzed Denitrogenative Transformations of Pyridotriazoles 281
Deepa Rawat, Abhisek Joshi, and Subbarayappa Adimurthy
11.1 Introduction 281
11.2 Rhodium-Catalyzed Transannulation of Pyridotriazoles 283
11.2.1 Rhodium-Catalyzed Transannulation of Pyridotriazoles with Alkyl Silane, Alkynes, and Nitriles 283
11.2.2 Rhodium-Catalyzed Transannulation of Pyridotriazoles with Amine and Amides 287
11.2.3 Rhodium-Catalyzed [4 + 3] Cycloaddition of Pyridotriazoles with 2-Phenylpyridine and S-Aryl Sulfoximines 288
11.2.4 Rhodium-Catalyzed Transannulation of Pyridotriazoles with 1,3-Dienes 290
11.2.5 Rhodium-Catalyzed Transannulation of Pyridotriazoles with N-Phenylbenzimidamides 291
11.2.6 Rhodium-Catalyzed [4 + 1] Cycloaddition of Pyridotriazoles with Propargyl Alcohols 292
11.3 Palladium-Catalyzed Ring-Opening of [1,2,3]Triazolo [1,5-a]pyridines 293
11.3.1 Palladium-Catalyzed Ring-Opening of Pyridotriazole with Aryl Halides 294
11.3.2 Palladium-Catalyzed Ring-Opening of Pyridotriazole with Acetic Anhydride 297
11.4 Copper-Catalyzed Denitrogenative Transannulation of Pyridotriazoles 299
11.4.1 Copper-Catalyzed Transannulation of Pyridotriazoles with Alkynes 299
11.4.2 Copper-Catalyzed Transannulation of Pyridotriazoles with Amines and Amino Acids 300
11.5 Cobalt-Catalyzed Transannulation of Pyridotriazoles with Isothiocyanates and Xanthate Esters 302
11.6 Ruthenium-Catalyzed Transannulation of Pyridotriazoles with Naphthoquinones 303
11.7 Summary and Conclusion 305
Acknowledgments 306
References 306
12 Metal-Free Denitrogenative Transformation of Pyridotriazoles 309
Sharma Happy, Akash Ratwan, and Dongari Yadagiri
12.1 Introduction 309
12.2 Acid-Catalyzed Denitrogenative Transformation of Pyridotriazoles 309
12.2.1 Lewis-Acid Catalyzed Reactions 309
12.2.2 Brønsted Acid-Catalyzed Reactions 312
12.3 Denitrogenative Transformations of Pyridotriazoles for Forming C - C and C - X Bond 315
12.3.1 Coupling of Boronic Acids with Pyridotriazoles 315
12.3.2 Iodine and Bromine Promoted Transformations of Pyridotriazoles 315
12.4 Thermolysis and Photolysis of Pyridotriazoles 316
12.5 Light-Induced Transformations of Pyridotriazoles 319
12.6 Summary and Outlook 321
Acknowledgments 321
References 321
13 Recent Development in Denitrogenative Transannulation of Benzotriazoles 325
Mangal S. Yadav, Manoj K. Jaiswal, Tanu Gupta, and Vinod K. Tiwari
13.1 Introduction 325
13.2 Common Route for the Synthesis of Benzotriazole Precursors 328
13.3 Transannulation of Benzotriazole-Appended Scaffolds 330
13.4 Conclusions and Future Perspective 349
Acknowledgments 350
References 350
14 Denitrogenative Transannulation of Thiadiazoles 359
Phil Ho Lee
14.1 Introduction 359
14.2 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Alkynes 359
14.2.1 Rh-Catalyzed Thiavinyl Carbenes from 1,2,3-Thiadiazoles for the Synthesis of Multisubstituted Thiophenes 359
14.2.2 Rh-Catalyzed Intramolecular Transannulation Reaction of Alkynyl Thiadiazoles for the Synthesis of 5,n-fused Thiophenes 361
14.2.3 Rh-Catalyzed Denitrogenative Transformations of 1,2,3-Thiadiazoles for the Synthesis of Multisubstituted Furans and Thiophenes 361
14.2.4 Rh-Catalyzed 1,1-Hydroacylation of Thioacyl Carbenes with Alkynyl Aldehydes and Subsequent Cyclization for the Synthesis of 4H-Thiopyran-4-ones 362
14.3 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Alkenes 363
14.3.1 Regioselective Synthesis of Dihydrothiophenes and Thiophenes via the Rh-Catalyzed Transannulation of 1,2,3-Thiadiazoles with Alkenes 363
14.3.2 Ir-Catalyzed Diastereospecific and Enantioselective (3 + 2) Transannulations of 1,2,3-Thiadiazoles with Norbornenes 366
14.3.3 Rh-Catalyzed 1,1-Hydroacylation of Thioacyl Carbenes with Alkynyl Aldehydes and Subsequent Cyclization 367
14.4 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Carbonyl Compounds 368
14.4.1 Ag-Mediated Annulation of 5H-1,2,3-Thiadiazoles with 1,3-Dicarbonyls for the Synthesis of Polysubstituted Furans 368
14.5 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Nitriles 369
14.5.1 Rh-Catalyzed Transannulation of 1,2,3-Thiadiazoles with Nitriles for the Synthesis of Isothiazole 369
14.5.2 Synthesis of Bicyclic Isothiazoles via Intramolecular Rh-Catalyzed Transannulation of Cyanothiadiazoles 372
14.5.3 Rh-Catalyzed Highly Chemoselective and Diastereoselective (3 + 2) Transannulations of 1,2,3-Thiadiazoles with Cyanoepoxides 373
14.5.4 Transannulaction of 1,2,3-Thiadiazoles and Alk-2-enenitriles for the Synthesis of 3-(Alk-1-enyl)isothiazoles 374
14.6 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Imines 375
14.6.1 (2 + 2 + 2) Annulations of Thioketenes and Imines 375
14.7 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Phosphaalkynes 376
14.7.1 Rh-Catalyzed Cyclization Reactions of Thiadiazoles with Phosphaalkynes for the Synthesis of 1,3-Thiaphospholes 376
14.8 Rh-Catalyzed Reaction of 1,2,3-Thiadiazoles with Aziridines 377
14.8.1 Synthesis of Thiazolines via the Thioketene-Induced Ring Expansion of Aziridines 377
14.9 Conclusions 378
References 379
15 Denitrogenative Transformations of Benzotriazinones and Related Compounds 381
Ramaraju Korivi, Popuri Sureshbabu, Dhanip Kumar Sharma, and Subramaniyan Mannathan
15.1 Introduction 381
15.2 Metal-Catalyzed Denitrogenative Transformations 381
15.3 Nickel and Palladium-Catalyzed Denitrogenative Transannulation Reactions 382
15.3.1 Synthesis of Isoquinolones and Related Derivatives 382
15.3.2 Synthesis of Phenanthridinones 385
15.3.3 Synthesis of Isoindolin-1-ones and Related Derivatives 386
15.4 Nickel-Catalyzed Denitrogenative Cross-Coupling Reactions 388
15.4.1 Synthesis of ortho-Arylated, Alkylated, and Alkenylated Benzamides 388
15.4.2 Synthesis of Functionalized β-Aryl Ketones 392
15.5 Pd-Catalyzed Cross-Coupling Reactions 394
15.5.1 Synthesis of ortho-Arylated and Alkenylated Benzamides 394
15.5.2 Synthesis of ortho-Methylated Benzamides 394
15.6 Visible-Light-Mediated Denitrogenative Reactions 395
15.6.1 Synthesis of Isoquinolones 395
15.6.2 Synthesis of ortho-Phosphorylated Aryl Amides 396
15.6.3 Synthesis of ortho-Selenylated Benzamides 397
15.7 Metal-free Denitrogenative Transformations 398
15.7.1 Synthesis of N-Isoxazolyl-2-iodobenzamides and 4H-Tetrazolo[1,5-a] [1,4]-benzodiazepine-6-ones 398
15.7.2 Synthesis of 2-Hydroxy-N-substituted Benzamides 399
15.7.3 Synthesis of 1,2-Benzodithiol-3-ones 399
15.8 Thermolysis 400
15.9 Lewis-Acid-Mediated Denitrogenation Reactions 401
15.10 Electrochemical Denitrogenative Transformations 402
15.11 Related Compounds 403
15.11.1 Synthesis of 3-Iminothiaisoindoline-1,1-dioxides 403
15.11.2 Synthesis of 3,4-Dihydro-1,2-benzothiazine-1,1(2H)-dioxides 403
15.11.3 Synthesis of Biaryl Sultams 404
15.12 Conclusions and Outlook 406
References 407
16 Denitrogenative Transformations of 3-Aminoindazoles 413
Xin Li and Qiuling Song
16.1 Introduction 413
16.2 Coupling with Conjugated Unsaturated Systems 415
16.2.1 Coupling with Heterocycles and Arenes 415
16.2.2 Coupling with Ketene Dithioacetals 417
16.2.3 Coupling with Enamines 417
16.2.4 Cascade Radical Processes 418
16.3 Coupling with Thiols and Diselenides 419
16.4 Denitrogenative Transannulation of 3-Aminoindazoles 419
16.5 N - N Bond Cleavage of 3-Aminoindazoles 421
16.6 Conclusion and Outlook 423
References 424
17 Denitrogenative Transformations of Tetrazoles and Pyridotetrazoles 427
Sandip Kumar Das and Buddhadeb Chattopadhyay
17.1 Introduction 427
17.2 Rh-Catalyzed Denitrogenative Annulation of Monocyclic Tetrazoles 428
17.3 Ir-Catalyzed Denitrogenative C(sp 2) - H Amination of Pyridotetrazoles 429
17.4 Intermolecular Denitrogenative Annulation of Pyridotetrazoles via Mn-Nitrene Intermediate 432
17.5 Denitrogenative Transformation of Pyridotetrazoles via Metalloradical Mechanism 433
17.5.1 Intermolecular Denitrogenative Annulation of Pyridotetrazoles 433
17.5.2 Intramolecular Denitrogenative C(sp 3) - H Amination of Pyridotetrazoles 435
17.5.3 Iron-Catalyzed Intramolecular Denitrogenative Radical Rearrangement of Pyridotetrazoles 437
17.5.4 Iron-Catalyzed Intramolecular Denitrogenative Radical C(sp 2) - H Amination of Pyridotetrazoles 439
17.5.5 Iron-Catalyzed Intermolecular Benzylic C(sp 3) - H Amination 441
17.5.6 Iron-Catalyzed Intermolecular Denitrogenative C - N Cross-Coupling Reactions 443
17.6 Summary and Outlook 444
References 445
18 Radical Denitrogenative Transformations of Polynitrogen Heterocycles 447
Sanjeev Kumar and Vinaykumar Kanchupalli
18.1 Introduction 447
18.2 Radical Denitrogenation of Benzotriazinones and Benzothiatriazines 449
18.3 Radical Denitrogenation of Triazoles and Benzotriazoles 454
18.4 Radical Denitrogenation of Pyridotriazoles 467
18.5 Radical Denitrogenation of Substituted 3-Aminoindazoles 473
18.6 Summary and Outlook 479
References 479
19 Application of Denitrogenative Transformations in Synthesis of Natural Products 485
H. R. Lohitha and Vignesh Palani
19.1 Introduction 485
19.2 Enantioselective Synthesis of (R)-Cycloprodigiosin 485
19.3 Synthesis of Uhle’s Ketone 487
19.4 Total Synthesis of (+)-Lysergol 488
19.5 Total Synthesis of (-)-Chanoclavine I 489
19.6 Total Syntheses of Tuberostemospiroline and Stemona-Lactam R 490
19.7 Total Synthesis of (+)-Petromyroxol 491
19.8 Synthesis of (±)-GSK 1360707 493
19.9 Access to the Framework of Aspidosperma and Kopsia Indole Alkaloids 493
19.10 Total Synthesis of (±)-Aurantioclavine 495
19.11 Total Synthesis of Nakafuran- 8 496
19.12 Photo-Induced Denitrogenative Transformation to Assemble an Indole Alkaloid Framework 497
19.13 Total Synthesis of Newbouldine and Withasomnine 498
19.14 Conclusion 499
References 500
Index 503
