Kinetic Resolution of α,β-Unsaturated Sulfoxides via Rh-Catalyzed Asymmetric Hydrogenation.

Chiral sulfoxides serve as pivotal precursors for the synthesis of organic sulfides and hold significant application value in the biomedicine and organic synthesis. This work describes a Rh/(S,S)-f-spiroPhos-catalyzed asymmetric hydrogenation enabling highly efficient kinetic resolution of racemic α,β-unsaturated sulfoxides. By this strategy, a series of multisubstituted vinyl chiral sulfoxides with only sulfur chiral centers and chiral sulfoxides bearing both carbon and sulfur chiral centers can be simultaneously afforded with excellent diastereoselectivities and enantioselectivities (up to >20:1 dr, 99% ee). The selectivity factor (s) reaches up to 1057. Furthermore, the resulting hydrogenation products can be readily transformed into chiral sulfones, chiral thioethers and chiral sulfonamides without any erosion of ee values under mild conditions.