Enantiotopic Desymmetrization of a Cyclic endo-Peroxide by Asymmetric Dialkylzinc Addition

Abstract

The desymmetrization reaction is a common strategy to synthesize complex chiral molecules. The selective cleavage of ­carbon-carbon or carbon-heteroatom bonds is well known, whereas the enantioselective cleavage of heteroatom-heteroatom bonds has been used less extensively. We demonstrate the enantiotopic ­addition of dialkyl zinc reagents to a bicyclic endo-peroxide using chiral [2.2]paracyclophane-based N,O-ligands as a new approach to chiral 4-alkoxy-substituted cyclohexenones.

Key words

desymmetrization - peroxide - asymmetric addition - ­dialkyl zinc - Michael acceptors

References and Notes

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The Supporting Information containing general remarks, synthesis details, analytical details (NMR, IR, MS, HRMS, HPLC) and complete tabelaric results are available from the authors.