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Cobalt‐Catalyzed Asymmetric Alkylation of (Hetero)Arenes with Styrenes

Tao Qin, Guowei Lv, Huanran Miao, Meihui Guan, Chunlu Xu, Ge Zhang, Tao Xiong, Qian Zhang

2022Angewandte Chemie International Edition84 citationsDOI

Abstract

Abstract An efficient and general intermolecular Cobalt(II)‐catalyzed asymmetric alkylation of styrenes with (hetero)arenes including indoles, thiophene and electron rich arenes has been developed, providing straightforward access to enantioenriched alkyl(hetero)arenes with high enantioselectivity. Mechanistic studies suggest that the reaction underwent a CoH‐mediated hydrogen atom transfer (HAT) with alkenes, followed by a pivotal catalyst‐controlled S N 2‐like pathway between in situ generated organocobalt(IV) species and aromatic nucleophiles. This is the first CoH‐catalyzed asymmetric hydrofunctionalization using carbon nucleophiles, providing a new strategy for asymmetric Friedel–Crafts type alkylation.

Topics & Concepts

ChemistryAlkylationNucleophileCobaltCatalysisThiopheneEnantioselective synthesisAlkylFriedel–Crafts reactionCombinatorial chemistryOrganic chemistryMedicinal chemistryCatalytic C–H Functionalization MethodsAsymmetric Hydrogenation and CatalysisAsymmetric Synthesis and Catalysis
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