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

Liana Hie; Noah F Fine Nathel; Xin Hong; Yun-Fang Yang; Kendall N Houk; Neil K Garg

doi:10.1002/anie.201511486

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

Angew Chem Int Ed Engl. 2016 Feb 18;55(8):2810-4. doi: 10.1002/anie.201511486. Epub 2016 Jan 25.

Authors

Liana Hie¹, Noah F Fine Nathel¹, Xin Hong¹, Yun-Fang Yang¹, Kendall N Houk², Neil K Garg³

Affiliations

¹ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
² Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA. houk@chem.ucla.edu.
³ Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA. neilgarg@chem.ucla.edu.

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.

Keywords: C−O activation; density functional calculations; methyl esters; nickel catalysis; oxidative addition.

Publication types

Research Support, N.I.H., Extramural
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Carbon / chemistry*
Catalysis
Esters / chemistry*
Models, Molecular
Nickel / chemistry*
Oxygen / chemistry*

Substances

Esters
Carbon
Nickel
Oxygen

Abstract

Publication types

MeSH terms

Substances

Grants and funding