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Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3-Csp2 coupling.

ABSTRACT: Cross-electrophile coupling (XEC) reactions of aryl and alkyl electrophiles are appealing but limited to specific substrate classes. Here, we report electroreductive XEC of previously incompatible electrophiles including tertiary alkyl bromides, aryl chlorides, and aryl/vinyl triflates. Reactions rely on the merger of an electrochemically active complex that selectively reacts with alkyl bromides through 1e^- processes and an electrochemically inactive Ni⁰(phosphine) complex that selectively reacts with aryl electrophiles through 2e^- processes. Accessing Ni⁰(phosphine) intermediates is critical to the strategy but is often challenging. We uncover a previously unknown pathway for electrochemically generating these key complexes at mild potentials through a choreographed series of ligand-exchange reactions. The mild methodology is applied to the alkylation of a range of substrates including natural products and pharmaceuticals.

SUBMITTER: Hamby TB

PROVIDER: S-EPMC9260526 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3-Csp2 coupling.

Hamby Taylor B TB LaLama Matthew J MJ Sevov Christo S CS

Science (New York, N.Y.) 20220421 6591

Cross-electrophile coupling (XEC) reactions of aryl and alkyl electrophiles are appealing but limited to specific substrate classes. Here, we report electroreductive XEC of previously incompatible electrophiles including tertiary alkyl bromides, aryl chlorides, and aryl/vinyl triflates. Reactions rely on the merger of an electrochemically active complex that selectively reacts with alkyl bromides through 1e<sup>-</sup> processes and an electrochemically inactive Ni<sup>0</sup>(phosphine) complex ...[more]

PMID: 35446658

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