ABSTRACT Molecules containing a tertiary α‐hydroxy carbonyl moiety are vital building blocks for synthesizing pharmaceuticals and natural products. In this study, we present an efficient rhodium(I)‐catalyzed enantioselective allylation of α‐ketoesters, providing a direct route to tertiary α‐hydroxy esters. Operating at 5 °C, the method employs various α‐ketoesters and allylBpin reagents to deliver the enantiomerically enriched tertiary homoallylic α‐hydroxyesters bearing quaternary centers in high yields (up to 99%), excellent enantioselectivity (up to 98% ee), and diastereoselectivity (dr > 20:1). Demonstrating its synthetic utility, this protocol enables a five‐step linear synthesis of lactone 13 —a key precursor for anti‐HIV and anticancer nucleoside analogues—from homoallylic alcohol 5af in a remarkable 85% overall yield.
Yang et al. (Thu,) studied this question.