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Asymmetric Remote <i>meta</i>-C–H Activation Controlled by a Chiral Ligand

Hang Wang, Huiling Li, Xiahe Chen, Chunlin Zhou, Shangda Li, Yun‐Fang Yang, Gang Li

2022ACS Catalysis20 citationsDOI

Abstract

The use of a chiral ligand for stereocontrol has assisted the development of a number of asymmetric functionalization of proximal C–H bonds. Herein, we report a chiral ligand-controlled, asymmetric remote meta-C–H activation of arenes, leading to asymmetric C–H olefination and arylation of hydrocinnamic acid derivatives through desymmetrization with Ac-L-Phe-OH as the chiral ligand using a Pd(II) catalyst. The origins of the enantioselectivity were explained with density functional theory calculations. The larger distortion energy of the substrate part in the C–H bond activation transition structure S-TS1 is the major controlling factor that disfavors the formation of the S-enantiomer product.

Topics & Concepts

DesymmetrizationLigand (biochemistry)Enantioselective synthesisChemistryChiral ligandStereochemistryCatalysisEnantiomerSubstrate (aquarium)Density functional theoryAsymmetric inductionCombinatorial chemistryComputational chemistryOrganic chemistryReceptorGeologyOceanographyBiochemistryCatalytic C–H Functionalization MethodsSynthesis and Catalytic ReactionsCyclopropane Reaction Mechanisms
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