Nickel-Catalyzed Activation of Acyl C-O Bonds of Methyl Esters.
Nickel-Catalyzed Activation of Acyl C-O Bonds of Methyl Esters.
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DOI：
10.1002/anie.201511486
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发表时间：
2016-02-18
期刊：
影响因子：
--
通讯作者：
Garg NK
中科院分区：
文献类型：
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作者：
Hie L;Fine Nathel NF;Hong X;Yang YF;Houk KN;Garg NK
我们报道了通过氧化加成过程激活甲酯酰基C-O键的第一种催化方法。使用镍催化形成的氧化加成加合物经过原位捕获以提供苯胺产物。DFT计算用于支持所提出的反应机理，理解为什么脱羰不发生竞争性反应，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。
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, understand why decarbonylation does not occur competitively, and to elucidate the beneficial role of the substrate structure and Al(OtBu)3 additive on the kinetics and thermodynamics of the reaction.