Enantioselective Synthesis of Chiral 3‐Substituted‐3‐silylpropionic Esters via Rhodium/Bisphosphine‐Thiourea‐Catalyzed Asymmetric Hydrogenation

We have successfully developed the asymmetric hydrogenation of β‐silyl‐α,β‐unsaturated esters to prepare chiral 3‐substituted‐3‐silylpropionic ester products catalyzed by rhodium/bisphosphine‐thiourea (ZhaoPhos) with excellent results (up to 97% yield, >99% ee, 1500 TON). Moreover, our hydrogenation products can be efficiently converted to other important organic molecules, such as chiral ethyl (R)‐3‐hydroxy‐3‐phenylpropanoate or (R)‐3‐[dimethyl(phenyl)silyl]‐3‐phenylpropanoic acid.