Cobalt-Catalyzed Electroreductive Alkylation of Unactivated Alkyl Chlorides with Conjugated Olefins.

Autor: Al Zubaydi S; Department of Chemistry and Biochemistry, The Ohio State University, 151 West Woodruff Avenue, Columbus, OH 43210, USA., Onuigbo IO; Department of Chemistry and Biochemistry, The Ohio State University, 151 West Woodruff Avenue, Columbus, OH 43210, USA., Truesdell BL; Department of Chemistry and Biochemistry, The Ohio State University, 151 West Woodruff Avenue, Columbus, OH 43210, USA., Sevov CS; Department of Chemistry and Biochemistry, The Ohio State University, 151 West Woodruff Avenue, Columbus, OH 43210, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jan 02; Vol. 63 (1), pp. e202313830. Date of Electronic Publication: 2023 Nov 29.
DOI: 10.1002/anie.202313830
Abstrakt: Reactions of unactivated alkyl chlorides under mild and sustainable conditions are rare compared to those of alkyl bromides or iodides. As a result, synthetic methods capable of modifying the vast chemical space of chloroalkane reagents, wastes, and materials are limited. We report the cobalt-catalyzed reductive addition of unactivated alkyl chlorides to conjugated alkenes. Co-catalyzed activation of alkyl chlorides is performed under electroreductive conditions, and the resulting reactions constitute formal alkyl-alkyl bond formation. In addition to developing an operationally simple methodology, detailed mechanistic studies provide insights into the elementary steps of a proposed catalytic cycle. In particular, we propose a switch in the mechanism of C-Cl bond activation from nucleophilic substitution to halogen atom abstraction, which is critical for efficiently generating alkyl radicals. These mechanistic insights were leveraged in designing ligands that enable couplings of primary, secondary, and tertiary alkyl chlorides.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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