Cyclopropanes in Organic Synthesis

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