金（I）催化炔丙基酯反应中的化学选择性：来自密度泛函理论计算的见解
Chemoselectivity in Gold(I)-Catalyzed Propargyl Ester Reactions: Insights From DFT Calculations.
作者信息
Sun Qing, Hong Pan, Wei Dongdong, Wu Anan, Tan Kai, Lu Xin
机构信息
State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory for Theoretical and Computational Chemistry, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, China.
出版信息
Front Chem. 2019 Sep 6;7:609. doi: 10.3389/fchem.2019.00609. eCollection 2019.
Au-catalyzed propargyl ester reactions have been investigated by a comprehensive density functional theory (DFT) study. Our calculations explain the experimental observed chemoselectivity of Au-catalyzed propargyl ester reactions very well by considering all possible pathways both in the absence and presence of 1,2,3-triazole (TA). The "X-factor" of TA is disclosed to have triple effects on this reaction. First of all, it can stabilize and prevent rapid decomposition of the Au catalyst. Secondly, the existence of TA promotes the nucleophilic attack and alters the chemoselectivity of this reaction. Moreover, TA acts as a "relay" to promote the proton transfer.
通过全面的密度泛函理论（DFT）研究对金催化的炔丙基酯反应进行了考察。我们的计算通过考虑在不存在和存在1,2,3 - 三唑（TA）的情况下所有可能的途径，很好地解释了实验观察到的金催化炔丙基酯反应的化学选择性。已揭示TA的“X因素”对该反应有三重影响。首先，它可以稳定并防止金催化剂快速分解。其次，TA的存在促进亲核进攻并改变该反应的化学选择性。此外，TA充当“中继”以促进质子转移。
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