Chemodivergent Dehydrative Nucleophilic Substitutions of Diarylmethanols with 1‐Phenyl‐1 H ‐tetrazole‐5‐thiol Catalyzed by FeCl 3
Chemodivergent Dehydrative Nucleophilic Substitutions of Diarylmethanols with 1‐Phenyl‐1 H ‐tetrazole‐5‐thiol Catalyzed by FeCl 3
复制标题
FeCl 3 催化二芳基甲醇与 1-苯基-1 H-四唑-5-硫醇的化学趋异脱水亲核取代
DOI：
10.1002/ajoc.202000301
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发表时间：
2020
影响因子：
2.7
通讯作者：
Nakata Kenya
中科院分区：
文献类型：
--
作者：
Oda Ryoga;Nakata Kenya
以FeCl 3为催化剂，在MeNO 2中，通过改变反应温度，实现了二芳基甲醇与1-苯基-1H-四唑-5-硫醇的化学发散脱水亲核取代反应.发现硫亲核攻击发生，得到动力学控制的产物，其重排成化学控制的产物。各种二芳基甲醇可以应用于反应，而不管底物的芳环上的取代基。还揭示了几种烷基和杂芳基取代的苄醇的反应给出了中等至良好的产物产率。进行的对照实验表明，两种反应都以SN 1方式进行，并且用刘易斯酸加热对于重排是必要的。
Chemodivergent dehydrative nucleophilic substitutions of diarylmethanols with 1‐phenyl‐1H‐tetrazole‐5‐thiol were achieved using FeCl3as a catalyst in MeNO2by changing reaction temperature. It was found that sulfur nucleophilic attack occurred to afford kinetically controlled products that rearranged into thermodynamically controlled products. A variety of diarylmethanols could be applied to the reaction, irrespective of the substituents on the aromatic rings of the substrates. It was also revealed that the reactions of several kinds of alkyl‐ and heteroaryl‐substituted benzyl alcohols gave moderate to good product yields. The controlled experiments performed revealed that both reactions proceeded in an SN1 fashion and heating with a Lewis acid was necessary for rearrangement.