Vinyl Cations
Erschienen am 2. Dezember 2012
528 Seiten
978-0-323-14708-8 (ISBN)
Beschreibung
Vinyl Cations provides a comprehensive and detailed treatment of the reactive intermediate in which the electron-deficient carbon is an integral part of a ? unsaturation. This book emphasizes that the reaction through vinyl cations is a viable pathway among the multitude of mechanistic routes for vinylic substitution. The aryl, ethynyl, and allenyl cations from the viewpoint of direct solvolytic generation from appropriate allenyl precursors are briefly discussed. Other topics include the preparative aspects of electrophilic additions to alkynes, participation of allenyl bonds in solvolyses, and vinyl cations generated through diazonium ions. The nature of the cationic intermediates, migrations across the double bond, thiirenium ions, and species related to vinyl cations are likewise elaborated. This publication is beneficial to chemists and researchers concerned with vinyl cations.
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Inhalt
PrefaceAcknowledgment1. Introduction and Historical Background Text References2. Thermodynamics and Theoretical Calculations I. Thermodynamic Considerations II. Theoretical Calculations References3. Electrophilic Additions to Alkynes and Participation of the Triple Bond in Solvolysis I. Mechanisms of Electrophilic Additions to Alkynes II. Preparative Aspects of Electrophilic Additions to Alkynes III. Triple-Bond Participation in Solvolysis References4. Electrophilic Additions to Allenes and Participation of the Allenyl Bond in Solvolysis I. Additions to Allenes II. Participation of Allenyl Bonds in Solvolyses References5. Bond Heterolysis I. General Considerations II. Vinyl Cations Generated Via Diazonium Ions III. Direct Solvolytic Generation IV. Stabilized Vinyl Cations V. Alkylvinyl Substrates References6. Arylvinyl Cations Via Solvolysis I. Introduction II. Competing Substitution and Elimination Routes III. Structural and Medium Effects on the Solvolysis IV. Stereochemistry of Vinylic Solvolysis and the Structure of a-Arylvinyl Cations V. Nature of the Cationic Intermediates VI. ß-Aryl Rearrangement in Triarylvinyl Systems VII. Nonsolvolytic Methods for Generating a-Arylvinyl Cations from Vinylic Precursors References7. Rearrangement of Vinyl Cations I. General Considerations II. Migrations to the Double Bond III. Migrations Across the Double Bond References8. Spectroscopic Evidence for Vinyl Cations I. Alkynyl Cations II. Vinyl Cations III. Thiirenium Ions References9. Miscellaneous and Conclusions I. Synthetic Uses of Vinyl Cations II. Metal-Stabilized Vinyl Cations III. Species Related to Vinyl Cations IV. Conclusions and Prognosis ReferencesSubject Index
