Donor Acceptor Cyclopropanes in Organic Synthesis

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Donor–Acceptor Cyclopropanes in Organic Synthesis
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Contents
Preface
1. Introduction to the Chemistry of Donor–Acceptor Cyclopropanes: A Historical and Personal Perspective
	1.1 Introduction
	1.2 My Personal Entry to Donor–Acceptor Cyclopropanes
	1.3 A Few Principles of the Chemistry of Donor–Acceptor Cyclopropanes
	1.4 Remarks Regarding the Terminology Applied to the Use of Donor–Acceptor Cyclopropanes
	1.5 Conclusions
	Abbreviations
	References
2. Understanding the Reactivity of Donor–Acceptor Cyclopropanes: Structural and Electronic Analysis
	2.1 Introduction
	2.2 Activated Cyclopropanes
	2.3 Donor–Acceptor Cyclopropanes (DACs)
	2.4 Computational and Kinetic Investigations
	2.5 Concluding Remarks
	References
3. Cycloaddition and Annulation Reactions of Donor–Acceptor Cyclopropanes
	3.1 Introduction
	3.2 Formal [3+2]-Cycloaddition with Carbon–Carbon Multiple Bonds
		3.2.1 General Aspects
		3.2.2 Formal [3+2]-Cycloaddition with C=C Double Bond
		3.2.3 Formal [3+2]-Cycloaddition with Triple C≡C Bond
		3.2.4 [3+2]-Annulation with Aromatic C=C Bond
		3.2.5 [3+2]-Annulation of D–A Cyclopropanes Involving Aryl/Heteroaryl Donor Substituent
	3.3 Formal [3+2]-Cycloaddition with C=O and C=N Double Bond
		3.3.1 Formal [3+2]-Cycloaddition with C=O Double Bond
		3.3.2 Formal [3+2]-Cycloaddition with C=N Double Bond
	3.4 Formal [3+2]-Cycloaddition with Other Heteroatom X=Y Double Bonds
		3.4.1 Formal [3+2]-Cycloaddition with Cumulenes and Heterocumulenes
		3.4.2 Formal [3+2]-Cycloaddition with SCN and SeCN
		3.4.3 Formal [3+2]-Cycloaddition with C=S and C=Se Double Bonds
		3.4.4 Formal [3+2]-Cycloaddition with N=O and N=N Double Bonds
		3.4.5 Formal [3+2]-Cycloaddition with C≡N Triple Bonds in Nitriles
		3.4.6 Formal [3+2]-Cycloaddition and Other Reactions with Three-Membered Heterocycles
	3.5 Formal [3+3]-Cycloaddition and Annulation Reactions of D–A Cyclopropanes
		3.5.1 General Aspects
		3.5.2 [3+3]-Annulation with Aromatic Substrates as 1,3-Synthons
		3.5.3 [3+3]-Annulation with Allenes, Allyl, and Propargyl Derivatives
		3.5.4 [3+3]-Annulation with Mercaptoacetaldehyde
		3.5.5 [3+3]-Cycloaddition with Nitrones and Nitronates
		3.5.6 [3+3]-Annulation/Cycloaddition with Dinitrogen Substrates
		3.5.7 Formal [3+3]-Cycloaddition with Azides and Diazo Compounds
	3.6 Reactions of Formal [4+3]-Cycloaddition and Annulation with Diene and Heterodiene Systems
		3.6.1 Dienes as Traps for 1,3-Zwitterions
		3.6.2 Reactions of [4+3]-Cyclization with Heterodiene Systems and Their Analogs
	3.7 Other Formal [n+m]-Cycloaddition and Annulation Processes
		3.7.1 Formal [8+3]-Cycloaddition Reactions
		3.7.2 Other Formal Stepwise “High-Order” Cycloaddition/Annulation Reactions
		3.7.3 Formal [3+1]- and [3+1+1]-Cycloadditions
		3.7.4 Cycloaddition/Annulation Reactions Proceed via Generation of β-Styrylmalonates
		3.7.5 GaCl3-Mediated Cycloaddition/Annulation Reactions via Generation of 1,2-Zwitterionic Intermediates
	3.8 Cyclodimerization Reactions of D–A Cyclopropanes
	3.9 Miscellaneous Reactions, Stepwise Cyclization Reactions, Cyclizations with Involvement of Functional Groups
		3.9.1 Stepwise Cyclization Using Substrates with Two Nitrogen Atoms
		3.9.2 Some Other Cascade and Miscellaneous Formal Cycloaddition Reactions for Cyclopropanedicarboxylates
		3.9.3 Formal Cycloaddition and Cyclization Reactions for 2-Aryl D–A Cyclopropanes Containing Active Substituent in Ortho-Position
		3.9.4 Cyclization Reactions of D–A Cyclopropanes with Additional CHO Group in Donor Part
		3.9.5 Miscellaneous Cyclizations with Phenols and Nitrogen-Containing Heterocycles
		3.9.6 Some Cyclization Reactions of 1,1-Dicyano Cyclopropanes
		3.9.7 Miscellaneous Cyclizations with Sulfur Reagents
		3.9.8 Cyclizations of Cyclopropanes Containing Carbonyl Group as an Acceptor with Amine Reagents
		3.9.9 Miscellaneous Reactions
	Acknowledgments
	References
4. Activation of Donor–Acceptor Cyclopropanes under Covalent Organocatalysis: Enamine, Iminium, NHC, Phosphine and Tertiary Amine Catalysis
	4.1 Introduction
	4.2 Secondary Amine Catalysis: Enamine Activation
	4.3 Secondary Amine Catalysis: Iminium Ion Activation
	4.4 NHC Catalysis: Activation Through Breslow Intermediates
	4.5 Phosphine or Tertiary Amine Catalysis
	4.6 Conclusion
	Acknowledgments
	References
5. Ring-Opening 1,3-Bisfunctionalization of Donor–Acceptor Cyclopropanes
	5.1 Introduction
	5.2 Enantioselective 1,3-Dichlorination of Formyl Group-Containing Cyclopropanes
	5.3 Ring-Opening 1,3-Dichlorination of D–A Cyclopropanes
	5.4 1,3-Chlorochalcogenation of Cyclopropyl Carbaldehydes
	5.5 1,3-Bisfunctionalization of D–A Cyclopropanes with Arenes and Nitrosoaren
	5.6 1-Amino-3-Aminomethylation of D–A Cyclopropanes
	5.7 1,3-Halochalcogenation of D–A Cyclopropanes
	5.8 1,3-Aminobromination of D–A Cyclopropanes
	5.9 Reaction of D–A Cyclopropanes with 4,5-Diazaspiro[2.4]hept-4-enes
	5.10 Four-Component Coupling of D–A Cyclopropanes
	5.11 1,3-Aminochalcogenation of Donor–Acceptor Cyclopropanes
	5.12 1,3-Bisfunctionalization of Donor–Acceptor Containing Cyclopropyl Boronic Ester
	5.13 1,3-Halogenation–Peroxidation of D–A Cyclopropanes
	5.14 1,3-Aminothiolation of D–A Cyclopropanes Using Sulfenamides
	5.15 1,3-Bisarylation of D–A Cyclopropanes with Electron-Rich Arenes and Hypervalent Arylbismuth Reagents
	5.16 Conversion of D–A Cyclopropanes to β-Hydroxy Ketones
	5.17 1,3-Carbothiolation of D–A Cyclopropanes
	5.18 1,3-Haloamination of D–A Cyclopropanes Employing Copper Salt and N-Fluorobenzenesulfonimide
	5.19 Ring-Opening 1,3-Carbocarbonation of D–A Cyclopropanes
	5.20 1,3-Aminofunctionalization of D–A Cyclopropanes
	5.21 Conclusion
	References
6. Molecular Rearrangements in Donor–Acceptor Cyclopropanes
	6.1 Introduction
	6.2 Donor–Acceptor Cyclopropane Isomerizations to Alkenes (Cyclopropane–Propene Rearrangement)
	6.3 Vinylcyclopropane–Cyclopentene Rearrangement
	6.4 Cloke–Wilson Rearrangement and Related Processes
		6.4.1 Rearrangement of Acyl-substituted Cyclopropanes to 2,3-dihydrofurans
		6.4.2 The Cloke–Wilson Rearrangements Affording Pyrrole Derivatives
		6.4.3 The Related Rearrangements Affording Other Heterocycles
	6.5 Nazarov Reaction and its Homo-Version
	6.6 The Cope Rearrangement and Related Isomerizations of Donor–Acceptor Cyclopropanes
	6.7 Intramolecular Nucleophilic Ring Opening/Ring Closure and Related Process
	Acknowledgment
	References
7. Donor–Acceptor Cyclopropanes with an Amino Group as Donor
	7.1 Introduction
	7.2 Synthesis of DA Aminocyclopropanes
		7.2.1 Synthesis of DA Aminocyclopropanes from β-Dehydroamino Acids (Route A)
		7.2.2 Synthesis of DA Aminocyclopropanes from Enamines (Route B)
		7.2.3 Synthesis of DA Aminocyclopropanes from Acrylates (Route C)
		7.2.4 Synthesis of DA Aminocyclopropanes from Cyclopropene (Route D1)
		7.2.5 Synthesis of DA Aminocyclopropanes from 2-Haloethylidene Malonates (Route D2)
		7.2.6 Synthesis of DA Aminocyclopropanes from Cyclopropylamines (Route E)
	7.3 Ring-Opening Reactions of DA Aminocyclopropanes
		7.3.1 Intramolecular Ring-Opening of DA Aminocyclopropanes
		7.3.2 Intermolecular Ring-Opening of DA Aminocyclopropanes
	7.4 Formal Cycloaddition of DA Aminocyclopropanes
	7.5 Conclusion
	Abbreviations
	References
8. Reactivity of Cyclopropyl Monocarbonyls
	8.1 Introduction
	8.2 Associated Challenges
		8.2.1 Reduced Reactivity
		8.2.2 Diastereomers and Controlled Reactivity
	8.3 Perks of Having a Monocarbonyl Substituent on Cyclopropane
		8.3.1 DAC Monocarbonyls—Not Merely a Three-Carbon Synthon
		8.3.2 Two Nucleophilic and Two Electrophilic Sites
		8.3.3 Cyclopropane Mono-Carbonyls in Organocatalysis
	8.4 Methods for the Preparation of Cyclopropyl Monocarbonyls
		8.4.1 From Olefins
			8.4.1.1 Corey–Chaykovsky Reaction
			8.4.1.2 Hydroformylation of Cyclopropenes
			8.4.1.3 Ozonolysis of Vinyl Cyclopropanes
		8.4.2 From Homoaldol Adducts
		8.4.3 From Arylthio Cyclopropyl Carbaldehydes
		8.4.4 From Diazo Compounds
		8.4.5 From 1,2-Dicarbonyl Compounds
	8.5 Cyclopropyl Monocarbonyls in Important Heterocyclic Synthesis
		8.5.1 Metal Catalyzed Annulation Reactions of Cyclopropyl Monocarbonyls
		8.5.2 Ring Expansion and Ring-Opening Reactions of Cyclopropyl Monocarbonyls
	8.6 Application in Total Synthesis
	References
9. Chemistry of Aroyl- and Nitro-Substituted Donor–Acceptor Cyclopropanes
	9.1 Introduction
	9.2 Synthesis of Aroyl-Substituted D–A Cyclopropanes
	9.3 Synthetic Applications of Aroyl-Substituted D–A Cyclopropanes
		9.3.1 AlCl3 or SnCl4-Mediated Ring-Opening Reactions
		9.3.2 TiCl4-Mediated Ring-Opening Reactions
		9.3.3 Ring-Opening Reactions with Hydrazines
		9.3.4 Ring-Opening Reactions with 1-Naphthylamines
		9.3.5 (3 + 2) Annulations with Nitriles
		9.3.6 (3 + 3) Annulation with Mercaptoacetaldehyde
		9.3.7 Conversion of Aroyl-Substituted D–A Cyclopropanes into γ-Butyrolactone-Fused D–A Cyclopropanes and their Synthetic Applications
		9.3.8 Works from Yang and Sekar Research Groups
	9.4 Synthesis of Nitro-Substituted D–A Cyclopropanes
	9.5 Synthetic Applications of Nitro-Substituted D–A Cyclopropanes
		9.5.1 BF3-Mediated Ring-Opening Reactions
		9.5.2 Reactions with Nitriles
		9.5.3 Reactions with Activated Aromatics
		9.5.4 Reaction with Mercaptoacetaldehyde Dimer
		9.5.5 Ring-Opening Reactions with 2-Aminopyridines
		9.5.6 Works from He, Xia, and Asahara Groups
	9.6 Conclusion
	Acknowledgments
	References
10. Metal-Free Activation of the Donor–Acceptor Cyclopropanes: Protic Acids, Bases, and Thermal Reactions
	10.1 Introduction
	10.2 Metal-Free Electrophilic Activation of D–A Cyclopropanes
	10.3 Metal-Free Nucleophilic Activation of D–A Cyclopropanes
	10.4 Catalyst-Free Activation of D–A Cyclopropanes
	10.5 Metal-Free Activation of D–A Cyclopropanes via Radical, SET, and Photopr
	10.6 Conclusion
	References
11. Asymmetric Catalytic Activation of Donor–Acceptor Cyclopropanes
	11.1 Introduction
	11.2 Chiral Lewis Acid-Catalyzed Reactions of D–A Cyclopropanes
		11.2.1 Asymmetric Reactions of Two-Substituted Cyclopropane-1,1-Dicarboxylates
		11.2.2 Asymmetric Reactions of 2-Substituted Cyclopropane-1,1-Diketones
	11.3 Chiral Low-Valent Transition Metal Promoted Reactions of Vinyl Cyclopropanes
		11.3.1 Ring-Opening Reactions
		11.3.2 [3 + n] Annulations
	11.4 Chiral Organocatalytic Reactions of D–A Cyclopropanes and Miscellaneous
		11.4.1 Enamine/Iminium Catalysis Activation
		11.4.2 Brønsted Base Catalyst Activation
		11.4.3 Nucleophilic Catalyst Activation
		11.4.4 Brønsted Acid Catalyst Activation
		11.4.5 Radical Pathway
	11.5 Conclusion
	References
12. Application of Donor–Acceptor Cyclopropanes in Total Synthesis of Natural Products
	12.1 Introduction
	12.2 Synthesis of Alkaloids
	12.3 Synthesis of Terpene/Terpenoids
	12.4 Synthesis of Miscellaneous Natural Products
	12.5 Conclusion
	Acknowledgments
	References
Index