Insights into Ag(i)-catalyzed addition reactions of amino alcohols to electron-deficient olefins: competing mechanisms, role of catalyst, and origin of chemoselectivity.
Insights into Ag(i)-catalyzed addition reactions of amino alcohols to electron-deficient olefins: competing mechanisms, role of catalyst, and origin of chemoselectivity.
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DOI：
10.1039/c8ra09065c
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发表时间：
2018-11-28
期刊：
影响因子：
3.9
通讯作者：
Wei, Donghui
中科院分区：
文献类型：
--
作者：
Liu, Chunhui;Han, Peilin;Xie, Zhizhong;Xu, Zhihong;Wei, Donghui
采用密度泛函方法系统研究了Ag(i)催化的氨基醇与缺电子烯烃化学选择性加成反应生成o -加合物或n-加合物的竞争机理。计算表明AgHMDS/dppe与AgOAc/dppe催化体系可以发挥不同的作用，从而产生两种不同的产物。AgHMDS/dppe体系作为Brønsted碱，使氨基醇OH脱质子形成Ag-O键，从而形成o -加合物。相比而言，AgOAc/dppe体系主要作为Lewis酸与氨基醇的O和N原子配位，但由于其碱性较弱，不能作为Brønsted碱进一步激活OH基团。因此，AgOAc/dppe催化反应的机理与非催化反应相似，生成的n-加合物相同。所获得的见解将对合理设计各种协同催化的化学选择性加成反应，包括使用不受保护的氨基醇的亲核性较低的羟基具有重要意义。首次对Ag(i)催化的氨基醇与烯烃加成反应的化学选择性进行了预测。
The competing mechanisms of Ag(i)-catalyzed chemoselective addition reactions of amino alcohols and electron-deficient olefins leading to the O-adduct or N-adduct products were systematically studied with density functional theory methods. Calculations indicate that the AgHMDS/dppe versus AgOAc/dppe catalytic systems can play different roles and thereby generate two different products. The AgHMDS/dppe system works as a Brønsted base to deprotonate the amino alcohol OH to form the Ag–O bond, which leads to formation of the O-adduct. In contrast, the AgOAc/dppe system mainly acts as a Lewis acid to coordinate with O and N atoms of the amino alcohol, but it cannot act as the Brønsted base to further activate the OH group because of its weaker basicity. Therefore, the AgOAc/dppe catalyzed reaction has a mechanism that is similar to the non-catalyzed reaction, and generates the same N-adduct. The obtained insights will be important for rational design of the various kinds of cooperatively catalyzed chemoselective addition reactions, including the use of the less nucleophilic hydroxyl groups of unprotected amino alcohols. The origin of the chemoselectivities of Ag(i)-catalyzed addition reactions of amino alcohols to olefin has been predicted for the first time.
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