Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University, Nanchang 330063, China.
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China.
Dalton Trans. 2022 Mar 1;51(9):3734-3739. doi: 10.1039/d1dt04028f.
The mechanism of Au(I)-catalyzed intermolecular annulation of 2-(1-alkynyl)-2-alken-1-one with -allenamide was carefully elucidated using density functional theory (DFT). The reaction is initiated by the binding of the Au(I) catalyst with 2-(1-alkynyl)-2-alken-1-one rather than with -allenamide. The key intermediate, a gold all-carbon 1,3-dipole species, is revealed to be more reactive than the gold allylic carbocation. The influence of ligands and substituents was rationally analyzed. We believe that our study will provide deeper mechanistic insights into the chemoselective reactions of alkynes with -allenamide.
使用密度泛函理论（DFT）详细阐明了 Au(I)催化 2-(1-炔基)-2-烯-1-酮与 -allenamide 进行分子间环化反应的机理。该反应是由 Au(I)催化剂与 2-(1-炔基)-2-烯-1-酮而不是与 -allenamide 结合引发的。关键中间体是一个金全碳 1,3-偶极子物种，其反应活性比金烯丙基碳正离子更高。合理分析了配体和取代基的影响。我们相信，我们的研究将为炔烃与 -allenamide 的选择性反应提供更深入的机理见解。
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