12. Cyclopropyl Radicals, Anion Radicals and Anions

  1. Zvi Rappoport
  1. Gernot Boche1 and
  2. Harry M. Walborsky2

Published Online: 28 JAN 2005

DOI: 10.1002/0470023449.ch12

Cyclopropyl Group: Volume 1 and Volume 2 (1987)

Cyclopropyl Group: Volume 1 and Volume 2 (1987)

How to Cite

Boche, G. and Walborsky, H. M. (1987) Cyclopropyl Radicals, Anion Radicals and Anions, in Cyclopropyl Group: Volume 1 and Volume 2 (1987) (ed Z. Rappoport), John Wiley & Sons, Ltd, Chichester, UK. doi: 10.1002/0470023449.ch12

Editor Information

  1. The Hebrew University, Jerusalem, Israel

Author Information

  1. 1

    Fachbereich Chemie, Philipps-Universität Marburg, D-3550 Marburg, Federal Republic of Germany

  2. 2

    Chemistry Department, Florida State University, Tallahassee, Florida 32306-3006, USA

Publication History

  1. Published Online: 28 JAN 2005
  2. Published Print: 28 OCT 1987

Book Series:

  1. PATAI'S Chemistry of Functional Groups

Book Series Editors:

  1. Saul Patai

ISBN Information

Print ISBN: 9780471917380

Online ISBN: 9780470023440

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Summary

This chapter contains sections titled:

  • General Introduction

  • Cyclopropyl Radical

    • Structure

    • Reactivity

    • Stereochemistry

      • Effect of α-substituents

        • Theoretical Considerations

        • Fluorine

        • Methoxyl

        • Chlorine, Bromine and Iodine

        • Carbomethoxyl and Cyano

        • Methyl and Trifluoromethyl

        • Hydrogen and Deuterium

        • Trimethylsilyl

        • Phenyl and Vinyl

      • Effect of β-substituents

      • Regioselectivity of the Rapidly Inverting σ-radical

      • Rearrangements

      • Solvent Cage Reactions

      • Aggregates (Clusters)

  • Anion Radicals

    • Introduction

    • Electron Transfer to σ Bonds of Cyclopropyl Halides

      • Surface Reactions

        • Lithium Surface

        • Magnesium Surface

        • Zinc Surface

        • Mercury Surface

      • Dissolving Metal Reductions (Homogeneous)

        • Reductions in Liquid Ammonia

        • Reductions with Alkali Metal Naphthalenides

    • Electron Transfer to π-bonded Substituents of Cyclopropanes

      • Introduction

      • Reductive Cleavage of Cyclopropanes

        • Regioselectivity

        • Electron Transfer Catalyzed Stereoisomerization

        • Mechanism of Formation of Isomeric Acyclic Olefins

  • Anions

    • Introduction

    • Formation from Cyclopropane and Its Stereochemistry

      • Effect of Substituent

        • α-carbonyl and α-carboalkoxyl

        • α-cyano

        • α-isocyano

        • α-nitro

        • α-sulfonyl and Derivatives

        • α-triphenylphosphonium and α-phosphonyl

        • α-sulfide, α-sulfoxide and α-diphenylsulfonium

        • α-phenyl, α-vinyl and α-acetylene

        • α-trifluoromethyl

        • α-trimethylsilyl, Methyl, Chloro, Fluoro and Methoxyl

        • β-alkoxyl

        • α-substituent Effects: Theoretical Studies

    • Cyclopropyl–Allyl Anion Transformations

    • Synthetic Applications

  • Acknowledgement

  • References