Vinyl Cations

Vinyl Cations

1st Edition - January 1, 1979

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  • Editor: Peter Stang
  • eBook ISBN: 9780323147088

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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.

Table of Contents

  • Preface


    1. Introduction and Historical Background



    2. Thermodynamics and Theoretical Calculations

    I. Thermodynamic Considerations

    II. Theoretical Calculations


    3. 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


    4. Electrophilic Additions to Allenes and Participation of the Allenyl Bond in Solvolysis

    I. Additions to Allenes

    II. Participation of Allenyl Bonds in Solvolyses


    5. Bond Heterolysis

    I. General Considerations

    II. Vinyl Cations Generated Via Diazonium Ions

    III. Direct Solvolytic Generation

    IV. Stabilized Vinyl Cations

    V. Alkylvinyl Substrates


    6. 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 α-Arylvinyl Cations

    V. Nature of the Cationic Intermediates

    VI. β-Aryl Rearrangement in Triarylvinyl Systems

    VII. Nonsolvolytic Methods for Generating α-Arylvinyl Cations from Vinylic Precursors


    7. Rearrangement of Vinyl Cations

    I. General Considerations

    II. Migrations to the Double Bond

    III. Migrations Across the Double Bond


    8. Spectroscopic Evidence for Vinyl Cations

    I. Alkynyl Cations

    II. Vinyl Cations

    III. Thiirenium Ions


    9. Miscellaneous and Conclusions

    I. Synthetic Uses of Vinyl Cations

    II. Metal-Stabilized Vinyl Cations

    III. Species Related to Vinyl Cations

    IV. Conclusions and Prognosis


    Subject Index

Product details

  • No. of pages: 528
  • Language: English
  • Copyright: © Academic Press 1979
  • Published: January 1, 1979
  • Imprint: Academic Press
  • eBook ISBN: 9780323147088

About the Editor

Peter Stang

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