Mechanistic Perspectives in the Regioselective Indole Addition to Unsymmetrical Silyloxyallyl Cations.
Mechanistic Perspectives in the Regioselective Indole Addition to Unsymmetrical Silyloxyallyl Cations.
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不对称甲硅烷氧基烯丙基阳离子区域选择性吲哚加成的机理观点。
DOI：
10.1021/acs.joc.9b00853
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Kartika,Rendy
中科院分区：
文献类型：
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作者：
Bresnahan,CaitlinG;Taylor-Edinbyrd,KiaraA;Cleveland,AlexanderH;Malone,JoshuaA;Dange,NitinS;Milet,Anne;Kumar,Revati;Kartika,Rendy
本文报道了吲哚与不对称硅氧基烯丙基阳离子加成反应的区域选择性机理。通过实验和计算方法，我们证实了硅醚基团的空间位阻效应对引导吲哚向内靠近的重要性，从而导致在较少取代的亲电α′-碳上的亲核攻击.残余水对加速反应速率的作用是通过稳定参与的甲硅烷基氧基烯丙基阳离子来建立的。
Our investigations on the reaction mechanism to account for regioselectivity on the addition of indoles to unsymmetrical silyloxyallyl cations are reported. Using both experimental and computational methods, we confirmed the significance of steric effects from the silyl ether group toward directing the inward approach of indoles, leading to nucleophilic attack at the less substituted electrophilic α′-carbon. The role of residual water toward accelerating the rate of reaction is established through stabilization of the participating silyloxyallyl cation.