Donor-Acceptor Cyclopropanes in Organic Synthesis

Prabal Banerjee, PhD, 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, PhD, 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.

• Preface xiii1 Introduction to the Chemistry of Donor–Acceptor Cyclopropanes: A Historical and Personal Perspective 1Hans-Ulrich Reissig1.1 Introduction 11.2 My Personal Entry to Donor–Acceptor Cyclopropanes 31.3 A Few Principles of the Chemistry of Donor–Acceptor Cyclopropanes 61.4 Remarks Regarding the Terminology Applied to the Use of Donor–Acceptor Cyclopropanes 101.5 Conclusions 12Abbreviations 12References 132 Understanding the Reactivity of Donor–Acceptor Cyclopropanes: Structural and Electronic Analysis 15Anu Jacob, Gwyndaf A. Oliver, and Daniel B. Werz2.1 Introduction 152.2 Activated Cyclopropanes 172.3 Donor–Acceptor Cyclopropanes (DACs) 192.4 Computational and Kinetic Investigations 222.5 Concluding Remarks 32References 323 Cycloaddition and Annulation Reactions of Donor–Acceptor Cyclopropanes 37Roman A. Novikov, Denis D. Borisov, and Yury V. Tomilov3.1 Introduction 373.2 Formal [3+2]-Cycloaddition with Carbon–Carbon Multiple Bonds 393.2.1 General Aspects 393.2.2 Formal [3+2]-Cycloaddition with C=C Double Bond 403.2.3 Formal [3+2]-Cycloaddition with Triple C≡C Bond 503.2.4 [3+2]-Annulation with Aromatic C=C Bond 533.2.5 [3+2]-Annulation of D–A Cyclopropanes Involving Aryl/Heteroaryl Donor Substituent 573.3 Formal [3+2]-Cycloaddition with C=O and C=N Double Bond 593.3.1 Formal [3+2]-Cycloaddition with C=O Double Bond 593.3.2 Formal [3+2]-Cycloaddition with C=N Double Bond 663.4 Formal [3+2]-Cycloaddition with Other Heteroatom X=Y Double Bonds 733.4.1 Formal [3+2]-Cycloaddition with Cumulenes and Heterocumulenes 733.4.2 Formal [3+2]-Cycloaddition with SCN and SeCN 763.4.3 Formal [3+2]-Cycloaddition with C=S and C=Se Double Bonds 773.4.4 Formal [3+2]-Cycloaddition with N=O and N=N Double Bonds 783.4.5 Formal [3+2]-Cycloaddition with C≡N Triple Bonds in Nitriles 803.4.6 Formal [3+2]-Cycloaddition and Other Reactions with Three-Membered Heterocycles 803.5 Formal [3+3]-Cycloaddition and Annulation Reactions of D–A Cyclopropanes 833.5.1 General Aspects 833.5.2 [3+3]-Annulation with Aromatic Substrates as 1,3-Synthons 843.5.3 [3+3]-Annulation with Allenes, Allyl, and Propargyl Derivatives 873.5.4 [3+3]-Annulation with Mercaptoacetaldehyde 883.5.5 [3+3]-Cycloaddition with Nitrones and Nitronates 893.5.6 [3+3]-Annulation/Cycloaddition with Dinitrogen Substrates 933.5.7 Formal [3+3]-Cycloaddition with Azides and Diazo Compounds 943.6 Reactions of Formal [4+3]-Cycloaddition and Annulation with Diene and Heterodiene Systems 963.6.1 Dienes as Traps for 1,3-Zwitterions 973.6.2 Reactions of [4+3]-Cyclization with Heterodiene Systems and Their Analogs 993.7 Other Formal [n+m]-Cycloaddition and Annulation Processes 1023.7.1 Formal [8+3]-Cycloaddition Reactions 1023.7.2 Other Formal Stepwise “High-Order” Cycloaddition/Annulation Reactions 1033.7.3 Formal [3+1]- and [3+1+1]-Cycloadditions 1053.7.4 Cycloaddition/Annulation Reactions Proceed via Generation of β-Styrylmalonates 1063.7.5 GaCl 3 -Mediated Cycloaddition/Annulation Reactions via Generation of 1,2-Zwitterionic Intermediates 1093.8 Cyclodimerization Reactions of D–A Cyclopropanes 1123.9 Miscellaneous Reactions, Stepwise Cyclization Reactions, Cyclizations with Involvement of Functional Groups 1183.9.1 Stepwise Cyclization Using Substrates with Two Nitrogen Atoms 1183.9.2 Some Other Cascade and Miscellaneous Formal Cycloaddition Reactions for Cyclopropanedicarboxylates 1193.9.3 Formal Cycloaddition and Cyclization Reactions for 2-Aryl D–A Cyclopropanes Containing Active Substituent in Ortho-Position 1223.9.4 Cyclization Reactions of D–A Cyclopropanes with Additional CHO Group in Donor Part 1233.9.5 Miscellaneous Cyclizations with Phenols and Nitrogen-Containing Heterocycles 1243.9.6 Some Cyclization Reactions of 1,1-Dicyano Cyclopropanes 1253.9.7 Miscellaneous Cyclizations with Sulfur Reagents 1263.9.8 Cyclizations of Cyclopropanes Containing Carbonyl Group as an Acceptor with Amine Reagents 1273.9.9 Miscellaneous Reactions 128References 1294 Activation of Donor–Acceptor Cyclopropanes under Covalent Organocatalysis: Enamine, Iminium, NHC, Phosphine and Tertiary Amine Catalysis 139Efraim Reyes, Liher Prieto, Luisa Carrillo, Uxue Uria, and Jose L. Vicario4.1 Introduction 1394.2 Secondary Amine Catalysis: Enamine Activation 1414.3 Secondary Amine Catalysis: Iminium Ion Activation 1444.4 NHC Catalysis: Activation Through Breslow Intermediates 1484.5 Phosphine or Tertiary Amine Catalysis 1574.6 Conclusion 162References 1625 Ring-Opening 1,3-Bisfunctionalization of Donor–Acceptor Cyclopropanes 167Avishek Guin and Akkattu T. Biju5.1 Introduction 1685.2 Enantioselective 1,3-Dichlorination of Formyl Group-Containing Cyclopropanes 1685.3 Ring-Opening 1,3-Dichlorination of D–A Cyclopropanes 1695.4 1,3-Chlorochalcogenation of Cyclopropyl Carbaldehydes 1705.5 1,3-Bisfunctionalization of D–A Cyclopropanes with Arenes and Nitrosoarenes 1725.6 1-Amino-3-Aminomethylation of D–A Cyclopropanes 1735.7 1,3-Halochalcogenation of D–A Cyclopropanes 1745.8 1,3-Aminobromination of D–A Cyclopropanes 1755.9 Reaction of D–A Cyclopropanes with 4,5-Diazaspiro[2.4] hept-4-enes 1765.10 Four-Component Coupling of D–A Cyclopropanes 1775.11 1,3-Aminochalcogenation of Donor–Acceptor Cyclopropanes 1785.12 1,3-Bisfunctionalization of Donor–Acceptor Containing Cyclopropyl Boronic Ester 1785.13 1,3-Halogenation–Peroxidation of D–A Cyclopropanes 1785.14 1,3-Aminothiolation of D–A Cyclopropanes Using Sulfenamides 1805.15 1,3-Bisarylation of D–A Cyclopropanes with Electron-Rich Arenes and Hypervalent Arylbismuth Reagents 1815.16 Conversion of D–A Cyclopropanes to β-Hydroxy Ketones 1825.17 1,3-Carbothiolation of D–A Cyclopropanes 1835.18 1,3-Haloamination of D–A Cyclopropanes Employing Copper Salt and N-Fluorobenzenesulfonimide 1845.19 Ring-Opening 1,3-Carbocarbonation of D–A Cyclopropanes 1855.20 1,3-Aminofunctionalization of D–A Cyclopropanes 1875.21 Conclusion 188References 1886 Molecular Rearrangements in Donor–Acceptor Cyclopropanes 191Igor V. Trushkov and Olga A. Ivanova6.1 Introduction 1916.2 Donor–Acceptor Cyclopropane Isomerizations to Alkenes (Cyclopropane–Propene Rearrangement) 1926.3 Vinylcyclopropane–Cyclopentene Rearrangement 1976.4 Cloke–Wilson Rearrangement and Related Processes 2026.4.1 Rearrangement of Acyl-substituted Cyclopropanes to 2,3-dihydrofurans 2026.4.2 The Cloke–Wilson Rearrangements Affording Pyrrole Derivatives 2086.4.3 The Related Rearrangements Affording Other Heterocycles 2096.5 Nazarov Reaction and its Homo-Version 2106.6 The Cope Rearrangement and Related Isomerizations of Donor– Acceptor Cyclopropanes 2156.7 Intramolecular Nucleophilic Ring Opening/Ring Closure and Related Processes 218References 2217 Donor–Acceptor Cyclopropanes with an Amino Group as Donor 227Ming-Ming Wang and Jerome Waser7.1 Introduction 2277.2 Synthesis of DA Aminocyclopropanes 2297.2.1 Synthesis of DA Aminocyclopropanes from β-Dehydroamino Acids (Route A) 2317.2.2 Synthesis of DA Aminocyclopropanes from Enamines (Route B) 2317.2.3 Synthesis of DA Aminocyclopropanes from Acrylates (Route C) 2337.2.4 Synthesis of DA Aminocyclopropanes from Cyclopropene (Route D1) 2337.2.5 Synthesis of DA Aminocyclopropanes from 2-Haloethylidene Malonates (Route D2) 2337.2.6 Synthesis of DA Aminocyclopropanes from Cyclopropylamines (Route E) 2347.3 Ring-Opening Reactions of DA Aminocyclopropanes 2357.3.1 Intramolecular Ring-Opening of DA Aminocyclopropanes 2367.3.2 Intermolecular Ring-Opening of DA Aminocyclopropanes 2407.4 Formal Cycloaddition of DA Aminocyclopropanes 2447.5 Conclusion 250Abbreviations 250References 2518 Reactivity of Cyclopropyl Monocarbonyls 255Pankaj Kumar, Irshad Maajid Taily, Priyanka Singh, and Prabal Banerjee8.1 Introduction 2558.2 Associated Challenges 2568.2.1 Reduced Reactivity 2568.2.2 Diastereomers and Controlled Reactivity 2578.3 Perks of Having a Monocarbonyl Substituent on Cyclopropane 2588.3.1 DAC Monocarbonyls— Not Merely a Three-Carbon Synthon 2588.3.2 Two Nucleophilic and Two Electrophilic Sites 2588.3.3 Cyclopropane Mono-Carbonyls in Organocatalysis 2598.4 Methods for the Preparation of Cyclopropyl Monocarbonyls 2608.4.1 From Olefins 2608.4.1.1 Corey–Chaykovsky Reaction 2608.4.1.2 Hydroformylation of Cyclopropenes 2618.4.1.3 Ozonolysis of Vinyl Cyclopropanes 2618.4.2 From Homoaldol Adducts 2618.4.3 From Arylthio Cyclopropyl Carbaldehydes 2628.4.4 From Diazo Compounds 2628.4.5 From 1,2-Dicarbonyl Compounds 2638.5 Cyclopropyl Monocarbonyls in Important Heterocyclic Synthesis 2648.5.1 Metal Catalyzed Annulation Reactions of Cyclopropyl Monocarbonyls 2648.5.2 Ring Expansion and Ring-Opening Reactions of Cyclopropyl Monocarbonyls 2678.6 Application in Total Synthesis 270References 2709 Chemistry of Aroyl- and Nitro-Substituted Donor–Acceptor Cyclopropanes 273Thangavel Selvi and Kannupal Srinivasan9.1 Introduction 2739.2 Synthesis of Aroyl-Substituted D–A Cyclopropanes 2749.3 Synthetic Applications of Aroyl-Substituted D–A Cyclopropanes 2769.3.1 AlCl 3 or SnCl 4 -Mediated Ring-Opening Reactions 2769.3.2 TiCl 4 -Mediated Ring-Opening Reactions 2789.3.3 Ring-Opening Reactions with Hydrazines 2789.3.4 Ring-Opening Reactions with 1-Naphthylamines 2809.3.5 (3 + 2) Annulations with Nitriles 2809.3.6 (3 + 3) Annulation with Mercaptoacetaldehyde 2829.3.7 Conversion of Aroyl-Substituted D–A Cyclopropanes into γ-Butyrolactone-Fused D–A Cyclopropanes and their Synthetic Applications 2859.3.8 Works from Yang and Sekar Research Groups 2869.4 Synthesis of Nitro-Substituted D–A Cyclopropanes 2899.5 Synthetic Applications of Nitro-Substituted D–A Cyclopropanes 2919.5.1 BF 3 -Mediated Ring-Opening Reactions 2919.5.2 Reactions with Nitriles 2929.5.3 Reactions with Activated Aromatics 2939.5.4 Reaction with Mercaptoacetaldehyde Dimer 2939.5.5 Ring-Opening Reactions with 2-Aminopyridines 2949.5.6 Works from He, Xia, and Asahara Groups 2969.6 Conclusion 297References 29810 Metal-Free Activation of the Donor–Acceptor Cyclopropanes: Protic Acids, Bases, and Thermal Reactions 301Lijia Wang and Yong Tang10.1 Introduction 30110.2 Metal-Free Electrophilic Activation of D–A Cyclopropanes 30210.3 Metal-Free Nucleophilic Activation of D–A Cyclopropanes 31310.4 Catalyst-Free Activation of D–A Cyclopropanes 31910.5 Metal-Free Activation of D–A Cyclopropanes via Radical, SET, and Photopromoted Process 32710.6 Conclusion 329References 33011 Asymmetric Catalytic Activation of Donor–Acceptor Cyclopropanes 333Yong Xia, Xiaohua Liu, and Xiaoming Feng11.1 Introduction 33311.2 Chiral Lewis Acid-Catalyzed Reactions of D–A Cyclopropanes 33411.2.1 Asymmetric Reactions of Two-Substituted Cyclopropane-1,1-Dicarboxylates 33411.2.1.1 Ring-Opening Reactions 33411.2.1.2 [3 + n] Annulations 33711.2.2 Asymmetric Reactions of 2-Substituted Cyclopropane-1,1-Diketones 34111.3 Chiral Low-Valent Transition Metal Promoted Reactions of Vinyl Cyclopropanes 34311.3.1 Ring-Opening Reactions 34411.3.2 [3 + n] Annulations 34511.4 Chiral Organocatalytic Reactions of D–A Cyclopropanes and Miscellaneous 34911.4.1 Enamine/Iminium Catalysis Activation 34911.4.2 Brønsted Base Catalyst Activation 35011.4.3 Nucleophilic Catalyst Activation 35111.4.4 Brønsted Acid Catalyst Activation 35211.4.5 Radical Pathway 35311.5 Conclusion 355References 35512 Application of Donor–Acceptor Cyclopropanes in Total Synthesis of Natural Products 359Amrita Saha, Karuna Mahato, Satysen Yadav, and Manas K. Ghorai12.1 Introduction 35912.2 Synthesis of Alkaloids 36012.3 Synthesis of Terpene/Terpenoids 37912.4 Synthesis of Miscellaneous Natural Products 40312.5 Conclusion 427References 427Index 433