Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system.
Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system.
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DOI：
10.1021/ja048688t
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发表时间：
2004-05
影响因子：
15
通讯作者：
M. Yasuda;S. Yamasaki;Y. Onishi;A. Baba
中科院分区：
文献类型：
--
作者：
M. Yasuda;S. Yamasaki;Y. Onishi;A. Baba
在苯甲醛存在下，InCl3催化醇与氯代二甲基硅烷(HSiMe2Cl)的反应，在温和的条件下得到相应的有机氯化物。苯并苯显著改变了反应过程，因为在没有苯并苯的情况下，通过脱羟基水合得到了还原产物。仲醇或叔醇被有效地氯化了。含有酸敏官能团的底物也被应用于该体系。在叔醇和伯醇的竞争反应中，观察到叔位的高选择性氯化反应。苯甲醛和HSiMe2Cl生成的高度配位的氢硅烷是一种重要的中间体。
The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate.