Mechanistic Study on Decarbonylative Phosphorylation of Aryl Amides by Nickel Catalysis
Mechanistic Study on Decarbonylative Phosphorylation of Aryl Amides by Nickel Catalysis
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镍催化芳基酰胺脱羰磷酸化反应机理研究
DOI：
10.1021/acs.joc.9b00962
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Yao Fu
中科院分区：
文献类型：
--
作者：
Yuantai Xu;Bing Wang;Julong Jiang;Haizhu Yu;Yao Fu
酰胺的磷酸化是一种前所未有的环境友好且易于实现的有机合成C-P键的方法。本研究采用密度泛函理论计算方法对Szostak等人最近报道的酰胺的镍催化直接脱羰基磷酸化反应的机理进行了系统的研究。反应主要经过四步：氧化加成（速率控制步骤）、磷酸化、脱羰基和还原消除。底物和Na 2CO 3的结构被认为是反应效率的关键。在底物中，酰胺键附近的羰基等吸电子基团通过削弱C-N键而促进了反应的进行，Na 2CO 3不仅可以中和磷酸酯配体中的H原子作为碱，还可以通过与酰胺键相邻羰基的配位键活化Ni-N键.
The phosphorylation of amide represents an unprecedented environmentally friendly and easily achievable method to constitute C–P bonds in organic synthesis. In this study, the mechanisms for the nickel-catalyzed direct decarbonylative phosphorylation of amides recently reported by Szostak’s team were systematically studied with density functional theory calculations. The reaction mainly undergoes four steps: oxidative addition (rate-determining step), phosphorylation, decarbonylation, and reductive elimination. The structures of the substrate and Na2CO3were found to be critical for the reaction efficiency. Substrates bearing electron-withdrawing groups like carbonyl groups near the amide bond facilitate the reaction by weakening the C–N bond, and Na2CO3can not only neutralize the H atom in the phosphate ligand as an alkali but also activate the Ni–N bond through the coordination bond with the adjacent carbonyl of the amide group.