title: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
authors.forename: Liana
authors.initials: L
authors.lastname: Hie
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
authors.forename: Noah F
authors.initials: NF
authors.lastname: Fine Nathel
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
authors.forename: Xin
authors.initials: X
authors.lastname: Hong
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
authors.forename: Yun-Fang
authors.initials: YF
authors.lastname: Yang
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA. houk@chem.ucla.edu.
authors.forename: Kendall N
authors.initials: KN
authors.lastname: Houk
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA. neilgarg@chem.ucla.edu.
authors.forename: Neil K
authors.initials: NK
authors.lastname: Garg
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D004952:Esters / Q000737:chemistry*; D008958:Models, Molecular; D009532:Nickel / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*
chemical_list: D004952:Esters; D002244:Carbon; D009532:Nickel; D010100:Oxygen
keywords: C−O activation; density functional calculations; methyl esters; nickel catalysis; oxidative addition