An Asymmetric Enzyme-Catalyzed Retro-Claisen Reaction for the Desymmetrization of Cyclicβ-Diketones

Abstract

Unsymmetrical is beautiful: Enzymatic desymmetrization offers a mild route to chiral synthons with, in principle, 100 % yield and absolute optical purity. The technique has been applied to bicyclic β-diketones for the first time, through a novel enzymatic retro-Claisen reaction, to yield chiral cyclic keto acids in up to 91 % yield and 94 % ee (see scheme, step a).