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Nickel-Catalyzed Activation of Acyl C-O Bonds of Methyl Esters.

ABSTRACT: We report the first catalytic method for activating the acyl C-O bonds of methyl esters through an oxidative-addition process. The oxidative-addition adducts, formed using nickel catalysis, undergo in?situ trapping to provide anilide products. DFT calculations are used to support the proposed reaction mechanism, to understand why decarbonylation does not occur competitively, and to elucidate the beneficial role of the substrate structure and the Al(OtBu)3 additive on the kinetics and thermodynamics of the reaction.

SUBMITTER: Hie L

PROVIDER: S-EPMC4821830 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

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Nickel-Catalyzed Activation of Acyl C-O Bonds of Methyl Esters.

Hie Liana L Fine Nathel Noah F NF Hong Xin X Yang Yun-Fang YF Houk Kendall N KN Garg Neil K NK

Angewandte Chemie (International ed. in English) 20160125 8

We report the first catalytic method for activating the acyl C-O bonds of methyl esters through an oxidative-addition process. The oxidative-addition adducts, formed using nickel catalysis, undergo in situ trapping to provide anilide products. DFT calculations are used to support the proposed reaction mechanism, to understand why decarbonylation does not occur competitively, and to elucidate the beneficial role of the substrate structure and the Al(OtBu)3 additive on the kinetics and thermodynam ...[more]

PMID: 26804615

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