Issue 2, 2023

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 activation and offers an additional chiral environment during the C–H cleavage.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
23 Sep 2022
Accepted
01 Dec 2022
First published
04 Dec 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 317-322

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

L. Kong, Y. Zou, X. Li, X. Zhang and X. Li, Chem. Sci., 2023, 14, 317 DOI: 10.1039/D2SC05310A

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