Advances in Carbene Chemistry, Volume 3
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Table of contents
- ADVANCES IN CARBENE CHEMISTRYiii
- Copyrightiv
- CONTENTSv
- LIST OF CONTRIBUTORSvii
- PREFACEix
- CARBENE PROTONATION1
- I. INTRODUCTION1
- II. CHEMICAL EVIDENCE FOR CARBENE PROTONATION3
- III. SPECTROSCOPIC EVIDENCE FOR CARBENE PROTONATION16
- IV. KINETIC EVIDENCE FOR CARBENE PROTONATION26
- V. BASICITY OF CARBENES35
- VI. CONCLUSION AND OUTLOOK44
- REFERENCES45
- KINETICS OF INTRAMOLECULAR CARBENE REACTIONS53
- I. INTRODUCTION54
- II. THE YLIDE METHOD54
- III. REARRANGEMENTS IN THE EXCITED STATE VS. CARBENE-ALKENE COMPLEXES57
- IV. QUANTUM MECHANICAL TUNNELING72
- V. KINETIC ISOTOPE EFFECTS77
- VI. SUBSTITUENT EFFECTS ON SINGLET CARBENE REARRANGEMENTS80
- VII. KINETICS OF 1,2-REARRANGEMENTS92
- ACKNOWLEDGEMENTS102
- APPENDIX102
- REFERENCES110
- CARBENES IN MATRICES: SPECTROSCOPY, STRUCTURE, AND PHOTOCHEMICAL BEHAVIOR115
- I. INTRODUCTION116
- II. BACKGROUND117
- III. INDIVIDUAL CARBENES118
- IV. ANALOGS OF CARBENES144
- V. CONCLUSION150
- ACKNOWLEDGEMENTS150
- REFERENCES150
- REACTIONS OF 2,5-CYCLOHEXADIENYLIDENES INVESTIGATED BY DIRECT SPECTROSCOPIC METHODS159
- I. INTRODUCTION160
- II. 4-OXOCYCLOHEXA-2,5-DIENYLIDENE AND DERIVATIVES161
- III. OTHER CYCLOHEXADIENYLIDENES193
- ACKNOWLEDGEMENTS199
- REFERENCES199
- DIFFERENCES BETWEEN PHENYLCARBENE AND PHENYLNITRENE AND THE RING EXPANSION REACTIONS THEY UNDERGO205
- I. INTRODUCTION206
- II. EXPERIMENTAL AND EARLY THEORETICAL STUDIES206
- III. COMPUTATIONAL RESULTS ON THE MECHANISMS OF RING EXPANSION216
- IV. WHY ARE NITRENES MORE STABLE THAN CARBENES?234
- V. SUBSTITUENT EFFECTS ON THE RATES AND REGIOCHEMISTRY OF THE RING EXPANSION OF PHENYLNITRENE239
- VI. CONCLUSIONS246
- ACKNOWLEDGEMENTS247
- REFERENCES247
- PHOTOACOUSTIC CALORIMETRY OF CARBENES253
- I. INTRODUCTION253
- II. BACKGROUND254
- III. INSTRUMENTATION258
- IV. EXPERIMENTAL RESULTS260
- V. CONCLUSIONS265
- ACKNOWLEDGEMENTS266
- REFERENCES266
- SOME ASPECTS OF THE CARBENE BRIDGEHEAD–OLEFIN CARBENE REARRANGEMENT269
- I. INTRODUCTION269
- II. RECENT COMPUTATIONAL CONTRIBUTIONS TO THE FIELD271
- III. EXPERIMENTAL RESULTS276
- ACKNOWLEDGEMENTS284
- REFERENCES284
- INSERTION OF CARBENES INTO C—H BONDS OF ALKOXIDES287
- I. INTRODUCTION287
- II. REGIOSELECTIVITY OF THE CARBENE INSERTION INTO α C–H BONDS OF ALKOXIDES289
- III. STEREOCHEMISTRY OF THE OXYANION-PROMOTED C–H INSERTION REACTION301
- IV. OTHER CARBENE REACTIONS FOUND IN THE STUDY OF INSERTION REACTIONS309
- V. SUMMARY313
- REFERENCES315
- KEYWORD INDEX317
Our understanding of carbene chemistry has advanced dramatically, especially in the last decade, and new developments continue to emerge. Some of the recent exciting findings have been collected in the first and second volumes of "Advances in Carbene Chemistry". With the third volume, the series continues to provide a periodic coverage of carbene chemistry in its broadest sense.
Beginning as chemical curiosities, carbenes are now solidly established as reactive intermediates with fascinating and productive research areas of their own. Five decades of divalent carbon chemistry have provided us with a vast repertoire of new, unusual, and surprising reactions. Some of those reactions, once classified as exotic, have become standard methods in organic synthesis. These highly reactive carbene species have been harnessed and put to work to achieve difficult synthetic tasks other reactive intermediates cannot easily perform.
The fruitful relationship between experiment and theory has pushed carbene chemistry further toward the direction of reaction control; that is, regio- and stereoselectivity in intra- and intermolecular addition and insertion reactions. The interplay between experiment and modern spectroscopy has led to the characterization of many carbenes that are crucial to both an understanding and further development of this field.
Beginning as chemical curiosities, carbenes are now solidly established as reactive intermediates with fascinating and productive research areas of their own. Five decades of divalent carbon chemistry have provided us with a vast repertoire of new, unusual, and surprising reactions. Some of those reactions, once classified as exotic, have become standard methods in organic synthesis. These highly reactive carbene species have been harnessed and put to work to achieve difficult synthetic tasks other reactive intermediates cannot easily perform.
The fruitful relationship between experiment and theory has pushed carbene chemistry further toward the direction of reaction control; that is, regio- and stereoselectivity in intra- and intermolecular addition and insertion reactions. The interplay between experiment and modern spectroscopy has led to the characterization of many carbenes that are crucial to both an understanding and further development of this field.