Facilitate milder, simpler reactions in organic synthesis with this cutting-edge family of building blocks
Donor-Accepted Cyclopropanes, or DACs, have attracted a resurgence of interest from organic chemists in recent decades for their role in facilitating various reactions such as cycloadditions, annulations, ring-opening and enantioselective transformations. The structural arrangement of DACs leads to milder, simpler reaction conditions, which have made them indispensable for a range of fundamentally and industrially important processes.
Donor-Acceptor Cyclopropanes in Organic Synthesis covers comprehensively the chemistry and applications of this compound class. The result is an invaluable guide for any researcher looking to bring DACs to bear in their own areas of research or development.
Readers will also find:
- A brief introduction of the history and reactivity of DACs
- Detailed discussion of reactions including Lewis acid-catalyzed cycloadditions, metal-free activation, asymmetric transformations, organocatalysis, and many more
- Application of DACs in natural product synthesis and pharmaceutical/agrochemical research
Donor-Acceptor Cyclopropanes in Organic Synthesis is ideal for organic chemists, experts in catalysis, pharmaceutical researchers, and any other scientists interested in facilitating milder, simpler reactions.
Cuprins
Preface xiii
1 Introduction to the Chemistry of Donor–Acceptor Cyclopropanes: A Historical and Personal Perspective 1
Hans-Ulrich Reissig
1.1 Introduction 1
1.2 My Personal Entry to Donor–Acceptor Cyclopropanes 3
1.3 A Few Principles of the Chemistry of Donor–Acceptor Cyclopropanes 6
1.4 Remarks Regarding the Terminology Applied to the Use of Donor–Acceptor Cyclopropanes 10
1.5 Conclusions 12
Abbreviations 12
References 13
2 Understanding the Reactivity of Donor–Acceptor Cyclopropanes: Structural and Electronic Analysis 15
Anu Jacob, Gwyndaf A. Oliver, and Daniel B. Werz
2.1 Introduction 15
2.2 Activated Cyclopropanes 17
2.3 Donor–Acceptor Cyclopropanes (DACs) 19
2.4 Computational and Kinetic Investigations 22
2.5 Concluding Remarks 32
References 32
3 Cycloaddition and Annulation Reactions of Donor–Acceptor Cyclopropanes 37
Roman A. Novikov, Denis D. Borisov, and Yury V. Tomilov
3.1 Introduction 37
3.2 Formal [3+2]-Cycloaddition with Carbon–Carbon Multiple Bonds 39
3.2.1 General Aspects 39
3.2.2 Formal [3+2]-Cycloaddition with C=C Double Bond 40
3.2.3 Formal [3+2]-Cycloaddition with Triple C≡C Bond 50
3.2.4 [3+2]-Annulation with Aromatic C=C Bond 53
3.2.5 [3+2]-Annulation of D–A Cyclopropanes Involving Aryl/Heteroaryl Donor Substituent 57
3.3 Formal [3+2]-Cycloaddition with C=O and C=N Double Bond 59
3.3.1 Formal [3+2]-Cycloaddition with C=O Double Bond 59
3.3.2 Formal [3+2]-Cycloaddition with C=N Double Bond 66
3.4 Formal [3+2]-Cycloaddition with Other Heteroatom X=Y Double Bonds 73
3.4.1 Formal [3+2]-Cycloaddition with Cumulenes and Heterocumulenes 73
3.4.2 Formal [3+2]-Cycloaddition with SCN and Se CN 76
3.4.3 Formal [3+2]-Cycloaddition with C=S and C=Se Double Bonds 77
3.4.4 Formal [3+2]-Cycloaddition with N=O and N=N Double Bonds 78
3.4.5 Formal [3+2]-Cycloaddition with C≡N Triple Bonds in Nitriles 80
3.4.6 Formal [3+2]-Cycloaddition and Other Reactions with Three-Membered Heterocycles 80
3.5 Formal [3+3]-Cycloaddition and Annulation Reactions of D–A Cyclopropanes 83
3.5.1 General Aspects 83
3.5.2 [3+3]-Annulation with Aromatic Substrates as 1, 3-Synthons 84
3.5.3 [3+3]-Annulation with Allenes, Allyl, and Propargyl Derivatives 87
3.5.4 [3+3]-Annulation with Mercaptoacetaldehyde 88
3.5.5 [3+3]-Cycloaddition with Nitrones and Nitronates 89
3.5.6 [3+3]-Annulation/Cycloaddition with Dinitrogen Substrates 93
3.5.7 Formal [3+3]-Cycloaddition with Azides and Diazo Compounds 94
3.6 Reactions of Formal [4+3]-Cycloaddition and Annulation with Diene and Heterodiene Systems 96
3.6.1 Dienes as Traps for 1, 3-Zwitterions 97
3.6.2 Reactions of [4+3]-Cyclization with Heterodiene Systems and Their Analogs 99
3.7 Other Formal [n+m]-Cycloaddition and Annulation Processes 102
3.7.1 Formal [8+3]-Cycloaddition Reactions 102
3.7.2 Other Formal Stepwise “High-Order” Cycloaddition/Annulation Reactions 103
3.7.3 Formal [3+1]- and [3+1+1]-Cycloadditions 105
3.7.4 Cycloaddition/Annulation Reactions Proceed via Generation of β-Styrylmalonates 106
3.7.5 Ga Cl 3 -Mediated Cycloaddition/Annulation Reactions via Generation of 1, 2-Zwitterionic Intermediates 109
3.8 Cyclodimerization Reactions of D–A Cyclopropanes 112
3.9 Miscellaneous Reactions, Stepwise Cyclization Reactions, Cyclizations with Involvement of Functional Groups 118
3.9.1 Stepwise Cyclization Using Substrates with Two Nitrogen Atoms 118
3.9.2 Some Other Cascade and Miscellaneous Formal Cycloaddition Reactions for Cyclopropanedicarboxylates 119
3.9.3 Formal Cycloaddition and Cyclization Reactions for 2-Aryl D–A Cyclopropanes Containing Active Substituent in Ortho-Position 122
3.9.4 Cyclization Reactions of D–A Cyclopropanes with Additional CHO Group in Donor Part 123
3.9.5 Miscellaneous Cyclizations with Phenols and Nitrogen-Containing Heterocycles 124
3.9.6 Some Cyclization Reactions of 1, 1-Dicyano Cyclopropanes 125
3.9.7 Miscellaneous Cyclizations with Sulfur Reagents 126
3.9.8 Cyclizations of Cyclopropanes Containing Carbonyl Group as an Acceptor with Amine Reagents 127
3.9.9 Miscellaneous Reactions 128
References 129
4 Activation of Donor–Acceptor Cyclopropanes under Covalent Organocatalysis: Enamine, Iminium, NHC, Phosphine and Tertiary Amine Catalysis 139
Efraim Reyes, Liher Prieto, Luisa Carrillo, Uxue Uria, and Jose L. Vicario
4.1 Introduction 139
4.2 Secondary Amine Catalysis: Enamine Activation 141
4.3 Secondary Amine Catalysis: Iminium Ion Activation 144
4.4 NHC Catalysis: Activation Through Breslow Intermediates 148
4.5 Phosphine or Tertiary Amine Catalysis 157
4.6 Conclusion 162
References 162
5 Ring-Opening 1, 3-Bisfunctionalization of Donor–Acceptor Cyclopropanes 167
Avishek Guin and Akkattu T. Biju
5.1 Introduction 168
5.2 Enantioselective 1, 3-Dichlorination of Formyl Group-Containing Cyclopropanes 168
5.3 Ring-Opening 1, 3-Dichlorination of D–A Cyclopropanes 169
5.4 1, 3-Chlorochalcogenation of Cyclopropyl Carbaldehydes 170
5.5 1, 3-Bisfunctionalization of D–A Cyclopropanes with Arenes and Nitrosoarenes 172
5.6 1-Amino-3-Aminomethylation of D–A Cyclopropanes 173
5.7 1, 3-Halochalcogenation of D–A Cyclopropanes 174
5.8 1, 3-Aminobromination of D–A Cyclopropanes 175
5.9 Reaction of D–A Cyclopropanes with 4, 5-Diazaspiro[2.4] hept-4-enes 176
5.10 Four-Component Coupling of D–A Cyclopropanes 177
5.11 1, 3-Aminochalcogenation of Donor–Acceptor Cyclopropanes 178
5.12 1, 3-Bisfunctionalization of Donor–Acceptor Containing Cyclopropyl Boronic Ester 178
5.13 1, 3-Halogenation–Peroxidation of D–A Cyclopropanes 178
5.14 1, 3-Aminothiolation of D–A Cyclopropanes Using Sulfenamides 180
5.15 1, 3-Bisarylation of D–A Cyclopropanes with Electron-Rich Arenes and Hypervalent Arylbismuth Reagents 181
5.16 Conversion of D–A Cyclopropanes to β-Hydroxy Ketones 182
5.17 1, 3-Carbothiolation of D–A Cyclopropanes 183
5.18 1, 3-Haloamination of D–A Cyclopropanes Employing Copper Salt and N-Fluorobenzenesulfonimide 184
5.19 Ring-Opening 1, 3-Carbocarbonation of D–A Cyclopropanes 185
5.20 1, 3-Aminofunctionalization of D–A Cyclopropanes 187
5.21 Conclusion 188
References 188
6 Molecular Rearrangements in Donor–Acceptor Cyclopropanes 191
Igor V. Trushkov and Olga A. Ivanova
6.1 Introduction 191
6.2 Donor–Acceptor Cyclopropane Isomerizations to Alkenes (Cyclopropane–Propene Rearrangement) 192
6.3 Vinylcyclopropane–Cyclopentene Rearrangement 197
6.4 Cloke–Wilson Rearrangement and Related Processes 202
6.4.1 Rearrangement of Acyl-substituted Cyclopropanes to 2, 3-dihydrofurans 202
6.4.2 The Cloke–Wilson Rearrangements Affording Pyrrole Derivatives 208
6.4.3 The Related Rearrangements Affording Other Heterocycles 209
6.5 Nazarov Reaction and its Homo-Version 210
6.6 The Cope Rearrangement and Related Isomerizations of Donor– Acceptor Cyclopropanes 215
6.7 Intramolecular Nucleophilic Ring Opening/Ring Closure and Related Processes 218
References 221
7 Donor–Acceptor Cyclopropanes with an Amino Group as Donor 227
Ming-Ming Wang and Jerome Waser
7.1 Introduction 227
7.2 Synthesis of DA Aminocyclopropanes 229
7.2.1 Synthesis of DA Aminocyclopropanes from β-Dehydroamino Acids (Route A) 231
7.2.2 Synthesis of DA Aminocyclopropanes from Enamines (Route B) 231
7.2.3 Synthesis of DA Aminocyclopropanes from Acrylates (Route C) 233
7.2.4 Synthesis of DA Aminocyclopropanes from Cyclopropene (Route D1) 233
7.2.5 Synthesis of DA Aminocyclopropanes from 2-Haloethylidene Malonates (Route D2) 233
7.2.6 Synthesis of DA Aminocyclopropanes from Cyclopropylamines (Route E) 234
7.3 Ring-Opening Reactions of DA Aminocyclopropanes 235
7.3.1 Intramolecular Ring-Opening of DA Aminocyclopropanes 236
7.3.2 Intermolecular Ring-Opening of DA Aminocyclopropanes 240
7.4 Formal Cycloaddition of DA Aminocyclopropanes 244
7.5 Conclusion 250
Abbreviations 250
References 251
8 Reactivity of Cyclopropyl Monocarbonyls 255
Pankaj Kumar, Irshad Maajid Taily, Priyanka Singh, and Prabal Banerjee
8.1 Introduction 255
8.2 Associated Challenges 256
8.2.1 Reduced Reactivity 256
8.2.2 Diastereomers and Controlled Reactivity 257
8.3 Perks of Having a Monocarbonyl Substituent on Cyclopropane 258
8.3.1 DAC Monocarbonyls— Not Merely a Three-Carbon Synthon 258
8.3.2 Two Nucleophilic and Two Electrophilic Sites 258
8.3.3 Cyclopropane Mono-Carbonyls in Organocatalysis 259
8.4 Methods for the Preparation of Cyclopropyl Monocarbonyls 260
8.4.1 From Olefins 260
8.4.1.1 Corey–Chaykovsky Reaction 260
8.4.1.2 Hydroformylation of Cyclopropenes 261
8.4.1.3 Ozonolysis of Vinyl Cyclopropanes 261
8.4.2 From Homoaldol Adducts 261
8.4.3 From Arylthio Cyclopropyl Carbaldehydes 262
8.4.4 From Diazo Compounds 262
8.4.5 From 1, 2-Dicarbonyl Compounds 263
8.5 Cyclopropyl Monocarbonyls in Important Heterocyclic Synthesis 264
8.5.1 Metal Catalyzed Annulation Reactions of Cyclopropyl Monocarbonyls 264
8.5.2 Ring Expansion and Ring-Opening Reactions of Cyclopropyl Monocarbonyls 267
8.6 Application in Total Synthesis 270
References 270
9 Chemistry of Aroyl- and Nitro-Substituted Donor–Acceptor Cyclopropanes 273
Thangavel Selvi and Kannupal Srinivasan
9.1 Introduction 273
9.2 Synthesis of Aroyl-Substituted D–A Cyclopropanes 274
9.3 Synthetic Applications of Aroyl-Substituted D–A Cyclopropanes 276
9.3.1 Al Cl 3 or Sn Cl 4 -Mediated Ring-Opening Reactions 276
9.3.2 Ti Cl 4 -Mediated Ring-Opening Reactions 278
9.3.3 Ring-Opening Reactions with Hydrazines 278
9.3.4 Ring-Opening Reactions with 1-Naphthylamines 280
9.3.5 (3 + 2) Annulations with Nitriles 280
9.3.6 (3 + 3) Annulation with Mercaptoacetaldehyde 282
9.3.7 Conversion of Aroyl-Substituted D–A Cyclopropanes into γ-Butyrolactone-Fused D–A Cyclopropanes and their Synthetic Applications 285
9.3.8 Works from Yang and Sekar Research Groups 286
9.4 Synthesis of Nitro-Substituted D–A Cyclopropanes 289
9.5 Synthetic Applications of Nitro-Substituted D–A Cyclopropanes 291
9.5.1 BF 3 -Mediated Ring-Opening Reactions 291
9.5.2 Reactions with Nitriles 292
9.5.3 Reactions with Activated Aromatics 293
9.5.4 Reaction with Mercaptoacetaldehyde Dimer 293
9.5.5 Ring-Opening Reactions with 2-Aminopyridines 294
9.5.6 Works from He, Xia, and Asahara Groups 296
9.6 Conclusion 297
References 298
10 Metal-Free Activation of the Donor–Acceptor Cyclopropanes: Protic Acids, Bases, and Thermal Reactions 301
Lijia Wang and Yong Tang
10.1 Introduction 301
10.2 Metal-Free Electrophilic Activation of D–A Cyclopropanes 302
10.3 Metal-Free Nucleophilic Activation of D–A Cyclopropanes 313
10.4 Catalyst-Free Activation of D–A Cyclopropanes 319
10.5 Metal-Free Activation of D–A Cyclopropanes via Radical, SET, and Photopromoted Process 327
10.6 Conclusion 329
References 330
11 Asymmetric Catalytic Activation of Donor–Acceptor Cyclopropanes 333
Yong Xia, Xiaohua Liu, and Xiaoming Feng
11.1 Introduction 333
11.2 Chiral Lewis Acid-Catalyzed Reactions of D–A Cyclopropanes 334
11.2.1 Asymmetric Reactions of Two-Substituted Cyclopropane-1, 1-Dicarboxylates 334
11.2.1.1 Ring-Opening Reactions 334
11.2.1.2 [3 + n] Annulations 337
11.2.2 Asymmetric Reactions of 2-Substituted Cyclopropane-1, 1-Diketones 341
11.3 Chiral Low-Valent Transition Metal Promoted Reactions of Vinyl Cyclopropanes 343
11.3.1 Ring-Opening Reactions 344
11.3.2 [3 + n] Annulations 345
11.4 Chiral Organocatalytic Reactions of D–A Cyclopropanes and Miscellaneous 349
11.4.1 Enamine/Iminium Catalysis Activation 349
11.4.2 Brønsted Base Catalyst Activation 350
11.4.3 Nucleophilic Catalyst Activation 351
11.4.4 Brønsted Acid Catalyst Activation 352
11.4.5 Radical Pathway 353
11.5 Conclusion 355
References 355
12 Application of Donor–Acceptor Cyclopropanes in Total Synthesis of Natural Products 359
Amrita Saha, Karuna Mahato, Satysen Yadav, and Manas K. Ghorai
12.1 Introduction 359
12.2 Synthesis of Alkaloids 360
12.3 Synthesis of Terpene/Terpenoids 379
12.4 Synthesis of Miscellaneous Natural Products 403
12.5 Conclusion 427
References 427
Index 433
Despre autor
Prabal Banerjee, Ph D, is an Associate Professor in the Department of Chemistry at the Indian Institution of Technology Ropar, Bara Phool, India. His research focuses on cycloaddition reactions, asymmetric catalysis, and related subjects.
Akkattu T. Biju, Ph D, is a Professor in the Department of Organic Chemistry at the Indian Institute of Science, Bangalore, India. His research focuses on developing transition-metal-free reactions and asymmetric catalysis using N-heterocyclic carbenes.
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