Vinyl Cations

Preface

Acknowledgment


1. Introduction and Historical Background

Text

References


2. Thermodynamics and Theoretical Calculations

I. Thermodynamic Considerations

II. Theoretical Calculations

References


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

References


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

I. Additions to Allenes

II. Participation of Allenyl Bonds in Solvolyses

References


5. Bond Heterolysis

I. General Considerations

II. Vinyl Cations Generated Via Diazonium Ions

III. Direct Solvolytic Generation

IV. Stabilized Vinyl Cations

V. Alkylvinyl Substrates

References


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

References


7. Rearrangement of Vinyl Cations

I. General Considerations

II. Migrations to the Double Bond

III. Migrations Across the Double Bond

References


8. Spectroscopic Evidence for Vinyl Cations

I. Alkynyl Cations

II. Vinyl Cations

III. Thiirenium Ions

References


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

References

Subject Index