Highly Chemo- and Enantioselective Rh-Catalyzed Hydrogenation of β-Sulfonyl-α,β-unsaturated Ketones: Access to Chiral γ-Ketosulfones

Rh-catalyzed highly chemo- and enantioselective hydrogenation of beta-sulfonyl-alpha,beta-unsaturated ketones was first successfully developed. Remarkably, a variety of enantioenriched gamma-ketosulfones were generated in good to high yields with excellent chemo/enantioselectivities (82-99% yields, >99:1 chemoselectivity, 88 to >99% ee). Moreover, the gram-scale asymmetric hydrogenation was carried out smoothly in 97% yield and 97% ee. Preliminary DFT computations furnished a reasonable explanation for the high chemoselectivity and enantioselectivity.

Automated summary

A highly chemo- and enantioselective hydrogenation method for beta-sulfonyl-alpha,beta-unsaturated ketones was successfully developed, producing a variety of enantioenriched gamma-ketosulfones in good to high yields with excellent selectivities. Gram-scale asymmetric hydrogenation was carried out smoothly with high yields and selectivities. Preliminary DFT computations provided a reasonable explanation for the observed high chemoselectivity and enantioselectivity.