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

doi:10.1002/anie.202201967

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

Angew Chem Int Ed Engl. 2022 Jun 27;61(26):e202201967. doi: 10.1002/anie.202201967. Epub 2022 May 5.

Authors

Tao Qin¹, Guowei Lv¹, Huanran Miao¹, Meihui Guan¹, Chunlu Xu¹, Ge Zhang¹, Tao Xiong¹, Qian Zhang^{1

2}

Affiliations

¹ Jilin Province Key Laboratory of Organic Functional Molecular Design & Synthesis, Department of Chemistry, Northeast Normal University, Changchun, 130024, China.
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, China.

PMID: 35363410
DOI: 10.1002/anie.202201967

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.

Keywords: (Hetero)Aryl Nucleophiles; Alkylation; Asymmetric; Cobalt Catalysis; Hydrogen Atom Transfer.

Abstract

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