Asymmetric Synthesis of α-Keto Esters via Cu(II)-Catalyzed Aerobic Deacylation of Acetoacetate Alkylation Products: An Unusually Simple Synthetic Equivalent to the Glyoxylate Anion Synthon

Abstract

A simple and efficient method for the preparation of β-stereogenic α-keto esters is described using a copper(II)-catalyzed aerobic deacylation of substituted acetoacetate esters. The substrates for the title process arise from catalytic, enantioselective conjugate additions and alkylation reactions of acetoacetate esters. The mild conditions do not induce racemization of the incipient enolizable α-keto ester. The reaction is tolerant of esters, certain ketones, ketals, and nitro groups and utilizes inexpensive, readily available materials.