Hie Liana, Fine Nathel Noah F, Hong Xin, Yang Yun-Fang, Houk Kendall N, Garg Neil K
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, 90095, USA.
Angew Chem Int Ed Engl. 2016 Feb 18;55(8):2810-4. doi: 10.1002/anie.201511486. Epub 2016 Jan 25.
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.
我们报道了第一种通过氧化加成过程活化甲酯酰基C-O键的催化方法。使用镍催化形成的氧化加成加合物会进行原位捕获以提供酰苯胺产物。密度泛函理论（DFT）计算用于支持所提出的反应机理，理解脱羰为何没有竞争性地发生，并阐明底物结构和Al(OtBu)3添加剂对反应动力学和热力学的有益作用。
