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Asymmetric Synthesis of Chiral Cyclopropanes from Sulfoxonium Ylides Catalyzed by a Chiral-at-Metal Rh(III) Complex

Jixin Pian, Qingqing Chen, Yujiao Luo, Zhifei Zhao, Jichang Liu, Lin He, Shiwu Li

2022Organic Letters25 citationsDOI

Abstract

An enantioselective cyclopropanation reaction of sulfoxonium ylides with β,γ-unsaturated ketoesters catalyzed by a chiral rhodium catalyst has been realized. A variety of optically pure 1,2,3-trisubstituted cyclopropanes was synthesized in 48-89% yields, with up to 99% ee, and with dr >20:1. Furthermore, research shows that a weak coordination between the chiral rhodium catalyst and β,γ-unsaturated ketoesters was responsible for the high diastereoselectivity and enantioselectivity of the corresponding products.

Topics & Concepts

ChemistryCatalysisEnantioselective synthesisCombinatorial chemistryMetalStereochemistryOrganic chemistryComputational chemistryCyclopropane Reaction MechanismsCatalytic Alkyne ReactionsCatalytic C–H Functionalization Methods