Rhodium-catalyzed enantioselective C-H alkynylation of sulfoxides in diverse patterns: desymmetrization, kinetic resolution, and parallel kinetic resolution.

ABSTRACT: Rhodium-catalyzed enantioselective C-H alkynylation of achiral and racemic sulfoxides is disclosed with alkynyl bromide as the alkynylating reagent. A wide range of chiral sulfoxides have been constructed in good yield and excellent enantioselectivity (up to 99% ee, s-factor up to > 500) via desymmetrization, kinetic resolution, and parallel kinetic resolution under mild reaction conditions. The high enantioselectivity was rendered by the chiral cyclopentadienyl rhodium(iii) catalyst paired with a chiral carboxamide additive. The interactions between the chiral catalyst, the sulfoxide, and the chiral carboxylic amide during the C-H bond cleavage offer the asymmetric induction, which is validated by DFT calculations. The chiral carboxamide functions as a base to promote C-H ac

SUBMITTER: Kong L 

PROVIDER: S-EPMC9811495 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature