Contemporary Carbene Chemistry.
Title:
Contemporary Carbene Chemistry.
Author:
Moss, Robert A.
ISBN:
9781118730409
Personal Author:
Edition:
1st ed.
Physical Description:
1 online resource (606 pages)
Series:
Wiley Series of Reactive Intermediates in Chemistry and Biology
Contents:
CONTEMPORARY CARBENE CHEMISTRY -- COPYRIGHT -- CONTENTS -- PREFACE TO SERIES -- PREFACE -- CONTRIBUTORS -- PART 1 PROPERTIES AND REACTIONS OF CARBENES -- 1 CARBENE STABILITY -- 1.1 INTRODUCTION -- 1.2 BACKGROUND -- 1.2.1 Measures of Carbene Stability -- 1.2.2 Bonding and Orbital Interactions in Carbenes -- 1.2.3 Determining Carbene Stability -- 1.3 CARBENE STABILITY -- 1.3.1 Hydrocarbon-Substituted Carbenes -- 1.3.2 Substituted Phenylcarbenes -- 1.3.3 Heteroatom-Substituted Carbenes -- 1.3.4 Conjugated Heterocyclic Carbenes -- 1.3.5 Carbenes with Other Electron-Withdrawing Groups -- 1.3.6 Carbenes versus Ylides -- 1.4 CORRELATIONS INVOLVING CARBENE STABILITY -- 1.4.1 CSE versus Singlet-Triplet Gap -- 1.4.2 CSE (Singlet) versus Proton Affinities -- 1.4.3 CSE (Singlet) versus Carbene Reaction Rates -- 1.5 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 2 STABLE CARBENES -- 2.1 INTRODUCTION -- 2.2 TYPES OF STABLE CARBENES -- 2.2.1 Push-Push Carbenes -- 2.2.2 Push-Pull Carbenes -- 2.2.3 Abnormal Carbenes -- 2.3 SPECTROSCOPIC CHARACTERISTICS -- 2.4 CHEMICAL REACTIVITY -- 2.4.1 Heteroallenes/Electrophilic Traps -- 2.4.2 Lewis Acids: Boryl Compounds -- 2.4.3 Alkenes, Alkynes, and Nitriles -- 2.4.4 Carbon Monoxide and Isonitriles -- 2.4.5 X-H Activation -- 2.4.6 Homodiatomic Bond Activation -- 2.4.7 Elemental Allotropes and Other Reactive Species -- 2.5 CONCLUSIONS AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 3 ACID-BASE CHEMISTRY OF CARBENES -- 3.1 INTRODUCTION -- 3.2 SOLUTION pKas OF THE CONJUGATE ACIDS OF CARBENES -- 3.2.1 Experimental Methods in Aprotic Solvents -- 3.2.2 Experimental Methods in Aqueous Solution -- 3.2.3 Substituent Effects on pKa -- 3.2.4 Solvent Effects on pKa -- 3.3 GAS-PHASE BASICITIES AND PROTON AFFINITIES OF CARBENES -- 3.3.1 Experimental Methods -- 3.3.2 Heteroatom-Stabilized Carbenes.
3.3.3 Alkyl- and Aryl-Substituted Carbenes -- 3.3.4 Halocarbenes -- 3.4 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 4 COMPUTATIONAL METHODS FOR THE STUDY OF CARBENES AND THEIR EXCITED STATES -- 4.1 INTRODUCTION -- 4.2 CARBENES -- 4.3 REARRANGEMENT IN EXCITED STATES (RIES) -- 4.4 ADVANCES IN COMPUTATIONAL INVESTIGATIONS OF CARBENES -- 4.4.1 Configuration Interaction -- 4.4.2 Complete Active Space Self-Consistent Field (CASSCF) Theory -- 4.4.3 Coupled-Cluster Theory with Resolution-of-the-Identity Approximation ( RI-CC2) -- 4.4.4 Time-Dependent Density Functional Theory (TD-DFT) -- 4.4.5 Molecular Dynamics (MD) -- 4.5 THEORETICAL STUDIES OF THE PHOTOCHEMISTRY OF CARBENE PRECURSORS -- 4.6 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 5 DYNAMICS IN CARBENE REACTIONS -- 5.1 INTRODUCTION -- 5.1.1 Carbenes -- 5.1.2 Nonstatistical Reaction Dynamics -- 5.2 DYNAMICS OF CARBENE CYCLOADDITIONS TO ALKENES AND ALKYNES -- 5.2.1 Carbene Additions to Unstrained Alkenes -- 5.2.2 Carbene Additions to Strained π Systems -- 5.2.3 Carbene Additions to Strained σ Systems -- 5.3 DYNAMICS OF OTHER CARBENE-MEDIATED REACTIONS -- 5.3.1 Wolff Rearrangement -- 5.3.2 Photochemical Carbene Formation -- 5.4 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 6 ULTRAFAST KINETICS OF CARBENE REACTIONS -- 6.1 INTRODUCTION -- 6.2 ULTRAFAST UV-VIS STUDIES OF THE INTERMOLECULAR REACTIVITY OF p-BIPHENYLYLCARBENE (BpCH) -- 6.3 REARRANGEMENTS IN THE EXCITED STATE OF THE CARBENE PRECURSOR -- 6.4 DYNAMICS OF CARBENE VIBRATIONAL COOLING AND SOLVATION -- 6.5 INFLUENCE OF SOLVENT ON CARBENE INTERSYSTEM CROSSING RATES -- 6.6 ELECTRONICALLY EXCITED (OPEN SHELL) SINGLET CARBENES -- 6.7 PARENT PHENYLDIAZIRINE-MECHANISTIC ASPECTS OF SINGLET CARBENE FORMATION.
6.8 INFLUENCE OF HALO-SUBSTITUENT ELECTRON-DONATING CAPACITY ON DIAZIRINE DECAY IN THE FIRST EXCITED SINGLET STATE -- 6.9 THE INFLUENCE OF EXCITATION WAVELENGTH ON THE PHOTOCHEMISTRY OF DIAZIRINES -- 6.10 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 7 TUNNELING IN THE REACTIONS OF CARBENES AND OXACARBENES -- 7.1 INTRODUCTION: LIGHT- AND HEAVY-ATOM TUNNELING -- 7.2 ALKYL- AND HALOCARBENES -- 7.2.1 Cyclopropylcarbenes -- 7.2.2 Ethylidene and Phenylmethylcarbene -- 7.2.3 Methylchlorocarbene and Benzylchlorocarbene -- 7.2.4 tert-Butylchlorocarbene -- 7.2.5 1-Methylcyclobutylfluorocarbene -- 7.2.6 Noradamantylchlorocarbene -- 7.3 THE FORMOSE REACTION AND HYDROXYCARBENES -- 7.3.1 Hydroxymethylene -- 7.3.2 Methylhydroxycarbene and Tunneling Control -- 7.3.3 Arylhydroxycarbenes -- 7.3.4 Cyclopropylhydroxycarbene -- 7.4 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 8 CARBODICARBENES -- 8.1 INTRODUCTION -- 8.2 CARBODICARBENES WITH N-HETEROCYCLIC LIGANDS C(NHC)2 -- 8.3 TETRAAMINOALLENES AND "HIDDEN" CARBODICARBENES -- 8.4 BENT ALLENES -- 8.5 RELATED COMPOUNDS -- 8.6 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 9 CATALYTIC REACTIONS WITH N-MESITYL-SUBSTITUTED N-HETEROCYCLIC CARBENES -- 9.1 INTRODUCTION -- 9.1.1 Historical Background -- 9.1.2 State of the Art Prior to 2004 -- 9.1.3 N-Mesityl Catalysts as the Key Innovation -- 9.2 THE N-MESITYL GROUP: A MECHANISTIC ASPECT -- 9.2.1 Catalytic Generation of Reactive Species via N-Mesityl NHCs -- 9.2.2 The Kinetic Effect of the N-Mesityl Group -- 9.3 NHC CATALYSIS BY CLASS OF REACTIVE INTERMEDIATES -- 9.3.1 Acyl Anion Equivalent -- 9.3.2 Homoenolate Equivalent -- 9.3.3 Enolate Equivalent -- 9.3.4 Activated Carboxylate Equivalent -- 9.3.5 α,β-Unsaturated Activated Carboxylate Equivalent -- 9.4 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES.
10 SUPRAMOLECULAR CARBENE CHEMISTRY -- 10.1 INTRODUCTION -- 10.2 TYPES OF HOSTS USED IN SUPRAMOLECULAR CARBENE CHEMISTRY -- 10.2.1 Cyclodextrins -- 10.2.2 Hemicarcerands -- 10.2.3 Resorcin[4]arene-Based Cavitands -- 10.2.4 Octa Acid -- 10.2.5 Cucurbit[n]urils -- 10.2.6 Zeolites -- 10.3 CHOOSING THE RIGHT CARBENE GUEST -- 10.4 DIAZIRINES AS SUITABLE SUPRAMOLECULAR CARBENE PRECURSORS -- 10.5 ARCHITECTURE OF THE GUEST@HOST COMPLEX -- 10.6 CASE STUDIES -- 10.6.1 Carbenes with Available 1,2-H Shifts -- 10.6.2 (2-[1,3-Dioxolan-2-yl]phenyl)(4-phenylphenyl)carbene -- 10.6.3 4-Oxocyclohexa-2,5-dienylidene -- 10.6.4 Dichlorocarbene -- 10.6.5 Adamantylidene -- 10.6.6 3-Oxobicyclo[3.2.1]octan-8-ylidene -- 10.6.7 endo-3-Hydroxybicyclo[3.2.1]octan-8-ylidene -- 10.6.8 Ring Fragmentation and Expansion -- 10.6.9 Aryl(halo)carbenes -- 10.6.10 Fluoro(phenoxy)carbene -- 10.6.11 Persistent Triplet Carbenes -- 10.7 CONCLUSION AND OUTLOOK -- ACKNOWLEDGMENTS -- SUGGESTED READING -- REFERENCES -- PART 2 Metal Carbenes -- 11 MODERN LITHIUM CARBENOID CHEMISTRY -- 11.1 INTRODUCTION -- 11.2 STRUCTURAL FEATURES OF LITHIUM CARBENOIDS -- 11.3 LITHIUM HALIDE CARBENOIDS -- 11.3.1 Thermal and Kinetic Stability -- 11.3.2 Configurational Stability and Stereochemistry of the Coupling Reactions with Electrophiles -- 11.4 STRUCTURE-REACTIVITY RELATIONSHIPS -- 11.5 LITHIUM-OXYGEN CARBENOIDS -- 11.6 LITHIUM-NITROGEN CARBENOIDS -- 11.7 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 12 RHODIUM CARBENES -- 12.1 INTRODUCTION -- 12.2 OVERVIEW OF RHODIUM-CARBENOID INTERMEDIATES AND CHIRAL CATALYSTS -- 12.3 ENANTIOSELECTIVE CYCLOPROPANATION -- 12.4 CASCADE SEQUENCES INITIATED BY RHODIUM-CATALYZED CYCLOPROPANATION -- 12.5 ENANTIOSELECTIVE CYCLOPROPENATION -- 12.6 C-H FUNCTIONALIZATION BY CARBENOID-INDUCED C-H INSERTION -- 12.7 COMBINED C-H ACTIVATION/COPE REARRANGEMENT (CHCR).
12.8 FORMATION AND REACTIONS OF RHODIUM-BOUND YLIDES -- 12.9 VINYLOGOUS REACTIONS OF RHODIUM-VINYLCARBENOIDS -- 12.10 CONCLUSIONS AND FUTURE OUTLOOK -- SUGGESTED READING -- REFERENCES -- 13 RUTHENIUM CARBENES -- 13.1 INTRODUCTION -- 13.2 IMPROVED MECHANISTIC UNDERSTANDING -- 13.2.1 Background -- 13.2.2 Identification of Ruthenacyclobutane Intermediates in Alkene Metathesis -- 13.2.3 Conformational Dynamics "Windshield Wipering" -- 13.3 CATALYST DEVELOPMENT -- 13.3.1 Development of Phosphine-Free Catalysts -- 13.3.2 Decomposition of the Grubbs' Complex -- 13.4 ACHIEVING SELECTIVITY IN ALKENE METATHESIS -- 13.4.1 Enantioselective Metathesis with Ruthenium Carbenes -- 13.4.2 Site Selectivity Using Relay Ring-Closing Metathesis -- 13.4.3 Z-Selective Alkene Metathesis -- 13.5 APPLICATIONS -- 13.5.1 Selected Examples of Alkene Metathesis in the Total Synthesis of Natural Products -- 13.5.2 Applications of Metathesis in Aqueous Systems -- 13.5.3 Applications in Diversity-Oriented Synthesis -- 13.6 CONCLUSION AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 14 NUCLEOPHILIC CARBENES OF THE CHROMIUM TRIAD -- 14.1 INTRODUCTION -- 14.1.1 Discovery -- 14.1.2 Spectroscopic Properties -- 14.1.3 Metathesis Reactivity -- 14.2 CHROMIUM CARBENES -- 14.2.1 Cr(VI) Carbenes -- 14.2.2 Nucleophilic Cr(III) Carbenes -- 14.2.3 Supported Cr(IV) Carbenes -- 14.3 MOLYBDENUM CARBENES -- 14.3.1 Mo(VI) Imido-Alkylidene-bis-Alkoxide Compounds -- 14.3.2 Mo(VI) Imido-Alkylidene Pyrrolide Compounds -- 14.3.3 Other Nucleophilic Mo Carbenes -- 14.3.4 Supported Mo Alkylidenes -- 14.4 TUNGSTEN CARBENES -- 14.4.1 W(VI) Imido-Alkylidene-bis-Alkoxide Compounds -- 14.4.2 W(VI) Imido-Alkylidene Pyrrolide Compounds -- 14.4.3 Other Nucleophilic Tungsten Carbenes -- 14.5 CONCLUSIONS AND OUTLOOK -- SUGGESTED READING -- REFERENCES -- 15 COBALT-MEDIATED CARBENE TRANSFER REACTIONS.
15.1 INTRODUCTION.
Abstract:
Presents the most innovative results in carbene chemistry, setting the foundation for new discoveries and applications The discovery of stable carbenes has reinvigorated carbene chemistry research, with investigators seeking to develop carbenes into new useful catalysts and ligands. Presenting the most innovative and promising areas of carbene research over the past decade, this book explores newly discovered structural, catalytic, and organometallic aspects of carbene chemistry, with an emphasis on new and emerging synthetic applications. Contemporary Carbene Chemistry features contributions from an international team of pioneering carbene chemistry researchers. Collectively, these authors have highlighted the most interesting and promising areas of investigation in the field. The book is divided into two parts: Part 1, Properties and Reactions of Carbenes, explores new findings on carbene stability, acid-base behavior, and catalysis. Carbenic structure and reactivity are examined in chapters dedicated to stable carbenes, carbodicarbenes, carbenes as guests in supramolecular hosts, tunneling in carbene and oxacarbene reactions, and ultrafast kinetics of carbenes and their excited state precursors. Theoretical concerns are addressed in chapters on computational methods and dynamics applied to carbene reactions. Part 2, Metal Carbenes, is dedicated to the synthetic dimensions of carbenes, particularly the reactions and catalytic properties of metal carbenes. The authors discuss lithium, rhodium, ruthenium, chromium, molybdenum, tungsten, cobalt, and gold. All the chapters conclude with a summary of the current situation, new challenges on the horizon, and promising new research directions. A list of key reviews and suggestions for further reading also accompanies every chapter. Each volume of the Wiley Series on Reactive Intermediates
in Chemistry and Biology focuses on a specific reactive intermediate, offering a broad range of perspectives from leading experts that sets the stage for new applications and further discoveries.
Local Note:
Electronic reproduction. Ann Arbor, Michigan : ProQuest Ebook Central, 2017. Available via World Wide Web. Access may be limited to ProQuest Ebook Central affiliated libraries.
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