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

• Published in: Angewandte Chemie International Edition Vol. 55; no. 8; pp. 2810 - 2814
• Main Authors: Hie, Liana, Fine Nathel, Noah F., Hong, Xin, Yang, Yun-Fang, Houk, Kendall N., Garg, Neil K.
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 18.02.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Adducts; Carbon - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; C−O activation; density functional calculations; Esters; Esters - chemistry; methyl esters; Models, Molecular; Nickel; Nickel - chemistry; nickel catalysis; oxidative addition; Oxygen - chemistry; Physical Sciences; Reaction kinetics; Science & Technology; Thermodynamics; AZOLES; AMIDATIONS; CARBOXYLATES; ARYL ESTERS; TRIARYLMETHANES; CLEAVAGE; nickel catalysis; density functional calculations; CROSS-COUPLING REACTIONS; AMINES; C-O activation; CONSTRUCTION; methyl esters; CHEMOSELECTIVITY; oxidative addition; C−O activation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201511486

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. The acyl C−O bonds of methyl esters are activated through a nickel‐catalyzed oxidative‐addition process. The putative oxidative‐addition adducts are trapped in situ to provide anilides. DFT calculations support the proposed mechanism, explain why decarbonylation does not occur competitively, and elucidate the beneficial role of Al(OtBu)3 on the kinetics and thermodynamics of the reaction.