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Nickela-electrocatalyzed C-H Alkoxylation with Secondary Alcohols: Oxidation-Induced Reductive Elimination at Nickel(III).

ABSTRACT: Nickela-electrooxidative C-H alkoxylations with challenging secondary alcohols were accomplished in a fully dehydrogenative fashion, thereby avoiding stoichiometric chemical oxidants, with H2 as the only stoichiometric byproduct. The nickela-electrocatalyzed oxygenation proved viable with various (hetero)arenes, including naturally occurring secondary alcohols, without racemization. Detailed mechanistic investigation, including DFT calculations and cyclovoltammetric studies of a well-defined C-H activated nickel(III) intermediate, suggest an oxidation-induced reductive elimination at nickel(III).

SUBMITTER: Zhang SK

PROVIDER: S-EPMC7028089 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Nickela-electrocatalyzed C-H Alkoxylation with Secondary Alcohols: Oxidation-Induced Reductive Elimination at Nickel(III).

Zhang Shou-Kun SK Struwe Julia J Hu Lianrui L Ackermann Lutz L

Angewandte Chemie (International ed. in English) 20200116 8

Nickela-electrooxidative C-H alkoxylations with challenging secondary alcohols were accomplished in a fully dehydrogenative fashion, thereby avoiding stoichiometric chemical oxidants, with H<sub>2</sub> as the only stoichiometric byproduct. The nickela-electrocatalyzed oxygenation proved viable with various (hetero)arenes, including naturally occurring secondary alcohols, without racemization. Detailed mechanistic investigation, including DFT calculations and cyclovoltammetric studies of a well- ...[more]

PMID: 31729814

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