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Synthesis of S(IV)‐Stereogenic Chiral Thio‐Oxazolidinones via Palladium‐Catalyzed Asymmetric [3+2] Annulations

Bao‐Cheng Wang, Fang Hu, Jiahui Bai, Fen‐Ya Xiong, Peng Chen, Jianye Li, Ying Tan, Yinlong Guo, Wen‐Jing Xiao, Liang‐Qiu Lu

2024Angewandte Chemie International Edition31 citationsDOI

Abstract

Organic molecules bearing chiral sulfur stereocenters exert a great impact on asymmetric catalysis and synthesis, chiral drugs, and chiral materials. Compared with acyclic ones, the catalytic asymmetric synthesis of thio-heterocycles has largely lagged behind due to the lack of efficient synthetic strategies. Here we establish the first modular platform to access chiral thio-oxazolidinones via Pd-catalyzed asymmetric [3+2] annulations of vinylethylene carbonates with sulfinylanilines. This protocol is featured by readily available starting materials, and high enantio- and diastereoselectivity. In particular, an unusual effect of a non-chiral supporting ligand on the diastereoselectivity was observed. Possible reaction mechanisms and stereocontrol models were proposed.

Topics & Concepts

StereocenterThio-ChemistryCatalysisEnantioselective synthesisCombinatorial chemistryPalladiumStereochemistryChiral ligandOrganic chemistrySulfur-Based Synthesis TechniquesSynthesis and Catalytic ReactionsCatalytic C–H Functionalization Methods