Cyclopropanes in Organic Synthesis Kulinkovich/Cyclopropanes in Organic Synthesis

Kulinkovich Oleg G. Cyclopropanes in Organic Synthesis 2015 [pdf 431sc 418c. 32.47mb] This is a practical guidebook about cyclopropanes that thoroughly surveys derivatives and transformations, synthetic methods, and experimental efficiency as a gateway for further research and development in the field.• Provides comprehensive lists and synthetically-oriented synopses of cyclopropane chemistry review references along with publication data on applications in the syntheses of natural and related biologically active compounds• Acts as a resource to help readers better understand cyclopropane applications for the efficient realization of synthetically important organic transformations and popular experimental procedures• Includes new developments and up-to-date information that will lead to original methodologies for complex organic synthesis• Stresses universality, flexibility, and experimental efficiency of a strategy based on preparing cyclopropane derivatives and performing ring cleavage reactions with inexpensive reagents• Focuses on the synthetic potential of cyclopropane applications, for example the synthesis of natural compounds and other target-oriented syntheses via cyclopropane intermediaries, as well on their planning by retrosynthetic analysis Content: Preface ix Part I Reactivity and availability 1 Introduction, 1 Reference, 2 1 Structure and Reactivity of the Cyclopropane Species 3 1.1 Geometry and Bonding, 3 1.2 Energy, 4 1.3 Spectra, 5 1.4 Cyclopropyl Cations, 5 1.5 Cyclopropyl Anions, 6 1.6 Cyclopropyl Radicals, 7 1.7 Cyclopropylidenes, 7 1.8 Cyclopropylcarbinyl Cations, 8 1.9 Cyclopropylcarbinyl Anions, 8 1.10 Cyclopropylcarbinyl Radicals, 10 1.11 Cyclopropylcarbenes, 10 1.12 Conclusion, 11 References, 13 2 Ring Cleavage Reactions 15 2.1 Cyclopropyl Activation, 16 2.1.1 Halogen, Oxy, and Sulfur Substituted Cyclopropanes, 16 2.1.2 Alkylidenecyclopropanes, 19 2.2 Cyclopropylcarbinyl Activation, 23 2.2.1 Halogeno, Oxy, Acyl and Metallomethyl Cyclopropanes, 23 2.2.2 Alkylidenecyclopropanes, 27 2.2.3 Vinyl and Ethynyl Cyclopropanes, 29 2.2.4 1,2 ]Divinylcyclopropanes, 33 2.2.5 Acceptor Cyclopropanes, 35 2.2.6 Donor Cyclopropanes, 38 2.2.7 Donor Acceptor Cyclopropanes, 43 2.3 Conclusion, 48 References, 49 3 Synthesis of Cyclopropanes 57 3.1 1,3 ]Cyclization Reactions, 57 3.1.1 Cyclizations with Cleavage of Two Single Bonds, 58 3.1.2 Cyclizations with Cleavage of One Double Bond and One Single Bond, 59 3.1.3 Cyclizations with Cleavage of Two Double Bonds, 62 3.2 [2 + 1] Cyclization Reactions, 65 3.2.1 Cycloaddition of Carbene Equivalents to Olefins, 66 3.2.2 Coupling of 1,1 ]Carbodianion and 1,2 ]Carbodication Equivalents, 79 3.2.3 Coupling of 1,1 ]Carbodication and 1,2 ]Carbodianion Equivalents, 83 3.3 Addition Reactions to the Double Bond of Cyclopropenes, 88 3.4 Interconversion of Cyclopropanes, 90 3.5 Conclusion, 90 References, 90 Part Ii Synthetic Application 99 Introduction, 99 References, 100 4 Triangulation Retrosynthetic Analysis 103 4.1 Retrosynthetic Triangulation, 103 4.2 Conclusion, 108 References, 108 5 Acyclic Compounds 109 5.1 Formation of Carbon Substituents, 109 5.1.1 Nonactivated Cyclopropane Precursors, 109 5.1.2 Cyclopropylcarbinyl Activated Precursors, 112 5.1.3 Cooperatively Activated Precursors, 138 5.2 Formation of Olefin Groups, 139 5.2.1 Cyclopropylcarbinyl Activated Precursors, 139 5.2.2 Cyclopropyl Activated Precursors, 142 5.2.3 Fragmentation of the Cyclopropane Precursors, 146 5.2.4 Cooperatively Activated Cyclopropane Precursors, 147 5.3 Formation of Carbonyl Groups, 151 5.3.1 Cyclopropylcarbinyl Precursors, 151 5.3.2 Cooperatively Activated Precursors, 156 5.4 Retrosynthetic Account, 162 References, 163 6 Cyclobutane Derivatives 167 6.1 Grandisol Syntheses, 167 6.2 Cyclobutane Synthetic Intermediates, 169 6.3 Retrosynthetic Account, 183 References, 184 7 Cyclopentanes 187 7.1 Vinylcyclopropane Cyclopentene Rearrangement, 187 7.1.1 Cyclopropylcarbinyl Activated Precursors, 187 7.1.2 Cooperatively Activated Precursors, 188 7.2 Cycloaddition Reactions, 221 7.2.1 Cyclopropylcarbinyl Activated Precursors, 221 7.2.2 Cooperatively Activated Precursors, 221 7.3 Modification of Substituents, 223 7.3.1 N onactivated Cyclopropane Precursors, 223 7.3.2 Cyclopropylcarbinyl Activated Precursors, 224 7.3.3 Cooperatively Activated Precursors, 231 7.3.4 Fragmentation Reactions, 245 7.4 Retrosynthetic Account, 246 References, 246 8 Cyclohexanes 251 8.1 Intramolecular Cyclization Reactions, 251 8.2 Cycloaddition Reactions, 255 8.3 Modification of Substituents, 269 8.3.1 Cyclopropylcarbinyl Activated Precursors, 269 8.3.2 Cyclopropyl Activated Precursors, 275 8.3.3 Cooperatively Activated Precursors, 277 8.4 Retrosynthetic Account, 282 References, 283 9 Cycloheptanes 285 9.1 Divinylcyclopropane Cycloheptadiene Rearrangement, 285 9.2 Cycloaddition Reactions, 315 9.3 Modification of Substituents, 318 9.3.1 Nonactivated Cyclopropane Precursors, 318 9.3.2 Cyclopropylcarbinyl Activated Precursors, 318 9.3.3 Cyclopropyl Activated Precursors, 323 9.3.4 Cooperatively Activated Precursors, 325 9.4 Retrosynthetic Account, 329 References, 330 10 Cyclooctanes and Larger Carbocycles 333 10.1 Cycloaddition Reactions, 333 10.2 Modification of Substituents, 334 10.2.1 Cyclopropylcarbinyl Activated Precursors, 334 10.2.2 Cyclopropyl Activated Precursors, 338 10.3 Retrosynthetic Account, 340 References, 340 11 Heterocyclic Compounds 341 11.1 Intramolecular Cyclization Reactions, 341 11.1.1 Nonactivated Cyclopropane Precursors, 341 11.1.2 Cyclopropylcarbinyl Activated Precursors, 342 11.1.3 Cyclopropyl Activated Precursors, 378 11.1.4 Cooperatively Activated Precursors, 380 11.2 Cycloaddition Reactions, 387 11.2.1 Cyclopropylcarbinyl Activated Precursors, 387 11.2.2 Cooperatively Activated Precursors, 390 11.3 Modification of Substituents, 400 11.3.1 Cyclopropylcarbinyl Activated Substrates, 400 11.3.2 Cyclopropyl Activated Substrates, 402 11.3.3 Cooperatively Activated Substrates, 402 11.4 Retrosynthetic Account, 409 References, 410 CONCLUSION 415 AUTHOR Index 417 TITLE PAGE 5 COPYRIGHT PAGE 6 CONTENTS 7 PREFACE 11 PART I REACTIVITY AND AVAILABILITY 13 CHAPTER I STRUCTURE AND REACTIVITY OF THE CYCLOPROPANE SPECIES 15 1.1 GEOMETRY AND BONDING 15 1.2 ENERGY 16 1.3 SPECTRA 17 1.4 CYCLOPROPYL CATIONS 17 1.5 СYCLOPROPYL ANIONS 18 1.6 CYCLOPROPYL RADICALS 19 1.7 CYCLOPROPYLIDENES 19 1.8 CYCLOPROPYLCARBINYL CATIONS 20 1.9 CYCLOPROPYLCARBINYL ANIONS 20 1.10 CYCLOPROPYLCARBINYL RADICALS 22 1.11 CYCLOPROPYLCARBENES 22 1.12 CONCLUSION 23 REFERENCES 25 CHAPTER 2 RING CLEAVAGE REACTIONS 27 2.1 CYCLOPROPYL ACTIVATION 28 2.1.1 Halogen, Oxy, and Sulfur Substituted Cyclopropanes 28 2.1.2 Alkylidenecyclopropanes 31 2.2 CYCLOPROPYLCARBINYL ACTIVATION 35 2.2.1 Halogeno, Oxy, Acyl and Metallomethyl Cyclopropanes 35 2.2.2 Alkylidenecyclopropanes 39 2.2.3 Vinyl and Ethynyl Cyclopropanes 41 2.2.4 1,2-Divinylcyclopropanes 45 2.2.5 Acceptor Cyclopropanes 47 2.2.6 Donor Cyclopropanes 50 2.2.7 Donor–Acceptor Cyclopropanes 55 2.3 CONCLUSION 60 REFERENCES 61 CHAPTER 3 SYNTHESIS OF CYCLOPROPANES 69 3.1 1,3-CYCLIZATION REACTIONS 69 3.1.1 Cyclizations with Cleavage of Two Single Bonds 70 3.1.2 Cyclizations with Cleavage of One Double Bond and One Single Bond 71 3.1.3 Cyclizations with Cleavage of Two Double Bonds 74 3.2 [2+1] CYCLIZATION REACTIONS 77 3.2.1 Cycloaddition of Carbene Equivalents to Olefins 78 3.2.2 Coupling of 1,1-Carbodianion and 1,2-Carbodication Equivalents 91 3.2.3 Coupling of 1,1-Carbodication and 1,2-Carbodianion Equivalents 95 3.3 ADDITION REACTIONS TO THE DOUBLE BOND OF CYCLOPROPENES 100 3.4 INTERCONVERSION OF CYCLOPROPANES 102 3.5 CONCLUSION 102 REFERENCES 102 Part II SYNTHETIC APPLICATION 111 CHAPTER 4 TRIANGULATION RETROSYNTHETIC ANALYSIS 115 4.1 RETROSYNTHETIC TRIANGULATION 115 4.2 CONCLUSION 120 REFERENCES 120 CHAPTER 5 ACYCLIC COMPOUNDS 121 5.1 FORMATION OF CARBON SUBSTITUENTS 121 5.1.1 Nonactivated Cyclopropane Precursors 121 5.1.2 Cyclopropylcarbinyl Activated Precursors 124 5.1.3 Cooperatively Activated Precursors 150 5.2 FORMATION OF OLEFIN GROUPS 151 5.2.1 Cyclopropylcarbinyl Activated Precursors 151 5.2.2 Cyclopropyl Activated Precursors 154 5.2.3 Fragmentation of the Cyclopropane Precursors 158 5.2.4 Cooperatively Activated Cyclopropane Precursors 159 5.3 FORMATION OF CARBONYL GROUPS 163 5.3.1 Cyclopropylcarbinyl Precursors 163 5.3.2 Cooperatively Activated Precursors 168 5.4 RETROSYNTHETIC ACCOUNT 174 REFERENCES 175 CHAPTER 6 CYCLOBUTANE DERIVATIVES 179 6.1 GRANDISOL SYNTHESES 179 6.2 CYCLOBUTANE SYNTHETIC INTERMEDIATES 181 6.3 RETROSYNTHETIC ACCOUNT 195 REFERENCES 196 CHAPTER 7 CYCLOPENTANES 199 7.1 VINYLCYCLOPROPANE–CYCLOPENTENE REARRANGEMENT 199 7.1.1 Cyclopropylcarbinyl Activated Precursors 199 7.1.2 Cooperatively Activated Precursors 200 7.2 CYCLOADDITION REACTIONS 233 7.2.1 Cyclopropylcarbinyl Activated Precursors 233 7.2.2 Cooperatively Activated Precursors 233 7.3 MODIFICATION OF SUBSTITUENTS 235 7.3.1 Nonactivated Cyclopropane Precursors 235 7.3.2 Cyclopropylcarbinyl Activated Precursors 236 7.3.3 Cooperatively Activated Precursors 243 7.3.4 Fragmentation Reactions 257 7.4 RETROSYNTHETIC ACCOUNT 258 REFERENCES 258 CHAPTER 8 CYCLOHEXANES 263 8.1 INTRAMOLECULAR CYCLIZATION REACTIONS 263 8.2 CYCLOADDITION REACTIONS 267 8.3 MODIFICATION OF SUBSTITUENTS 281 8.3.1 Cyclopropylcarbinyl Activated Precursors 281 8.3.2 Cyclopropyl Activated Precursors 287 8.3.3 Cooperatively Activated Precursors 289 8.4 RETROSYNTHETIC ACCOUNT 294 REFERENCES 295 CHAPTER 9 CYCLOHEPTANES 297 9.1 DIVINYLCYCLOPROPANE–CYCLOHEPTADIENE REARRANGEMENT 297 9.2 CYCLOADDITION REACTIONS 327 9.3 MODIFICATION OF SUBSTITUENTS 330 9.3.1 Nonactivated Cyclopropane Precursors 330 9.3.2 Cyclopropylcarbinyl Activated Precursors 330 9.3.3 Cyclopropyl Activated Precursors 335 9.3.4 Cooperatively Activated Precursors 337 9.4 RETROSYNTHETIC ACCOUNT 341 REFERENCES 342 CHAPTER 10 CYCLOOCTANES AND LARGER CARBOCYCLES 345 10.1 CYCLOADDITION REACTIONS 345 10.2 MODIFICATION OF SUBSTITUENTS 346 10.2.1 Cyclopropylcarbinyl Activated Precursors 346 10.2.2 Cyclopropyl Activated Precursors 350 10.3 RETROSYNTHETIC ACCOUNT 352 REFERENCES 352 CHAPTER 11 HETEROCYCLIC COMPOUNDS 353 11.1 INTRAMOLECULAR CYCLIZATION REACTIONS 353 11.1.1 Nonactivated Cyclopropane Precursors 353 11.1.2 Cyclopropylcarbinyl Activated Precursors 354 11.1.3 Cyclopropyl Activated Precursors 390 11.1.4 Cooperatively Activated Precursors 392 11.2 CYCLOADDITION REACTIONS 399 11.2.1 Cyclopropylcarbinyl Activated Precursors 399 11.2.2 Cooperatively Activated Precursors 402 11.3 MODIFICATION OF SUBSTITUENTS 412 11.3.1 Cyclopropylcarbinyl Activated Substrates 412 11.3.2 Cyclopropyl Activated Substrates 414 11.3.3 Cooperatively Activated Substrates 414 11.4 RETROSYNTHETIC ACCOUNT 421 REFERENCES 422 CONCLUSION 427 AUTHOR INDEX 429 EULA 431

This is a practical guidebook about cyclopropanes that thoroughly surveys derivatives and transformations, synthetic methods, and experimental efficiency as a gateway for further research and development in the field. • Provides comprehensive lists and synthetically-oriented synopses of cyclopropane chemistry review references along with publication data on applications in the syntheses of natural and related biologically active compounds
• Acts as a resource to help readers better understand cyclopropane applications for the efficient realization of synthetically important organic transformations and popular experimental procedures
• Includes new developments and up-to-date information that will lead to original methodologies for complex organic synthesis
• Stresses universality, flexibility, and experimental efficiency of a strategy based on preparing cyclopropane derivatives and performing ring cleavage reactions with inexpensive reagents
• Focuses on the synthetic potential of cyclopropane applications, for example the synthesis of natural compounds and other target-oriented syntheses via cyclopropane intermediaries, as well on their planning by retrosynthetic analysis