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Hybrid Palladium Catalyst Assembled from Chiral Phosphoric Acid and Thioamide for Enantioselective β‐C(sp<sup>3</sup>)−H Arylation

Hua‐Jie Jiang, Xiu‐Mei Zhong, Ziye Liu, Rui‐Long Geng, Yangyang Li, Yun‐Dong Wu, Xinhao Zhang, Liu‐Zhu Gong

2020Angewandte Chemie International Edition50 citationsDOI

Abstract

Abstract A hybrid palladium catalyst assembled from a chiral phosphoric acid (CPA) and thioamide enables a highly efficient and enantioselective β‐C(sp 3 )−H functionalization of thioamides (up to 99 % yield, 97 % ee ). A kinetic resolution of unsymmetrical thioamides by intermolecular C(sp 3 )−H arylation can be achieved with high s‐factors. Mechanistic investigations have revealed that stereocontrol is achieved by embedding the substrate in a robust chiral cavity defined by the bulky CPA and a neutral thioamide ligand.

Topics & Concepts

ThioamideEnantioselective synthesisPalladiumPhosphoric acidCatalysisChemistryYield (engineering)Kinetic resolutionSubstrate (aquarium)StereochemistryOrganic chemistryCombinatorial chemistryMaterials scienceOceanographyGeologyMetallurgyCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsSynthetic Organic Chemistry Methods
Hybrid Palladium Catalyst Assembled from Chiral Phosphoric Acid and Thioamide for Enantioselective β‐C(sp<sup>3</sup>)−H Arylation | Litcius