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Nickel‐Catalyzed Activation of Acyl C−O Bonds of Methyl Esters
Author(s) -
Hie Liana,
Fine Nathel Noah F.,
Hong Xin,
Yang YunFang,
Houk Kendall N.,
Garg Neil K.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201511486
Subject(s) - decarbonylation , chemistry , catalysis , oxidative addition , nickel , substrate (aquarium) , adduct , reaction mechanism , kinetics , medicinal chemistry , photochemistry , stereochemistry , organic chemistry , oceanography , physics , quantum mechanics , geology
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.