Desymmetrization and Diastereotopic Group Selection in 1,4-Cyclohexadienes

Abstract

Diastereotopic group selection in 1,4-cyclohexadienes is a useful approach to synthesize rather complex compounds in a single operation. The stereoinduction occurs via a covalently bound stereogenic center. Cycloadditions, Michael additions, and radical reactions have been conducted as group-selective processes. Even more elegant is the desymmetrization of an achiral 1,4-cyclohexadiene. Various chiral reagents have been used successfully to desymmetrize 1,4-cyclohexadienes. In one step, at least two new stereogenic centers are formed. Chiral quaternary carbon centers can be obtained with high selectivity. This Account will provide an overview on diastereotopic group selection and desymmetrization in various 1,4-cyclohexadiene derivatives.

• 1 Introduction

• 2 Diastereotopic Group-Selective Processes

• 2.1 Cycloaddition

• 2.2 Michael Additions

• 2.3 Radical Processes

• 3 Desymmetrizations

• 3.1 Oxidations

• 3.2 Transition-Metal-Mediated Processes

• 3.3 Metalated Cyclohexadienes

• 4 Conclusions

Key words

asymmetric synthesis - catalysis - allylations - radical ­reactions - γ-butyrolactones

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34

The enantiomeric excess was determined by chiral HPLC.

35

Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Center as private communication no. CCDC-280946 [Klaus Harms, Private Communication(1078), 2005]. Copies of the data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road Cambridge CB2 1EZ, UK).