Chemoenzymatic synthesis of α′- and α-acetoxylated cyclic ketones

Abstract

α,β-Unsaturated and saturated cyclic ketones were selectively oxidized at the α′- and α-positions using Mn(OAc)3 and Pb(OAc)4, respectively, resulting in high chemical yields. The resultant racemic α′- and α-acetoxylated substrates were resolved into corresponding enantiomerically enriched α′- and α-hydroxylated and acetoxylated compounds with 96–98% ee via PLE hydrolysis. The absolute configurations of α′-acetoxy-α,β-unsaturated cyclic ketones were determined by transforming them into the corresponding saturated α-acetoxy cyclic ketones of known absolute configuration.