Synthetic Potential of Configurationally Unstable Chiral Carbanions

Michiko Sasaki; Kei Takeda

doi:10.1055/s-0031-1290440

Synlett, Table of Contents

Synlett 2012; 23(15): 2153-2164
DOI: 10.1055/s-0031-1290440

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Synthetic Potential of Configurationally Unstable Chiral Carbanions

Michiko Sasaki

Department of Synthetic Organic Chemistry, Graduate School of Biomedical and Health Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8553, Japan, Fax: +81(82)257-5184 Email: takedak@hiroshima-u.ac.jp

,

Kei Takeda*

Department of Synthetic Organic Chemistry, Graduate School of Biomedical and Health Sciences, Hiroshima University, 1-2-3 Kasumi, Minami-Ku, Hiroshima 734-8553, Japan, Fax: +81(82)257-5184 Email: takedak@hiroshima-u.ac.jp

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Abstract

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Abstract

This account summarizes our recent efforts in exploring the synthetic potential of configurationally labile chiral carbanions next to electron-withdrawing groups that have previously been considered to be impossible even to generate. We place particular emphasis on the generation and trapping of chiral α-nitrile carbanions as well as evaluation of the configurational stability of those carbanions and effects of solvent on the stability.

1 Introduction

2 Epoxysilane Rearrangement

2.1 Background

2.2 Chirality Transfer from Epoxide to Carbanion

2.3 Chirality Transfer from an Epoxide by [2,3]-Wittig Rearrangement and Trapping of a Chiral Carbanion

2.4 Solvent Effects on the Configurational Stability of Carbanions

3 Evaluation of the Effects of Substituents on Configurational Stability of a Chiral Carbanion

4 Enantioselective Trapping of an α-Chiral Carbanion of Acyclic Nitrile by a Carbon Electrophile

5 Summary

Key words

carbanions - nitriles - stereoselective synthesis - Brook rearrangement - Wittig rearrangement

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References

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