Highly Efficient Enantioselective Synthesis of Chiral Sulfones by Rh-Catalyzed Asymmetric Hydrogenation.

Abstract

A highly efficient and enantioselective Rh-( R, R)-f-spiroPhos complex catalyzed hydrogenation of a series of unsaturated sulfones has been developed. With Rh-( R, R)-f-spiroPhos catalyst under mild conditions, not only the asymmetric hydrogenation of both the 3,3-diaryl and exocyclic α,β-unsaturated sulfones was first realized with up to 99.9% ee but also 3-alkyl-3-aryl and benzo[ b]thiophene-1,1-dioxides were successfully hydrogenated to the corresponding chiral sulfones with excellent enantioselectivities (up to 99.4% ee) regardless of the steric hindrance, electronic property, and geometry of the substrates. Moreover, this reaction offers a route to ( S)-(+)- ar-turmerone as a spice flavor, which is an important synthetic intermediate of pharmaceuticals.