Organocatalytic chemo- and regioselective oxyarylation of styrenes via a cascade reaction: remote activation of hydroxyl groups.
Organocatalytic chemo- and regioselective oxyarylation of styrenes via a cascade reaction: remote activation of hydroxyl groups.
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DOI：
10.1021/jo500859b
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发表时间：
2014-06
期刊：
影响因子：
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通讯作者：
Yu-Chen Zhang;Fei Jiang;Shu‐Liang Wang;F. Shi;S. Tu
中科院分区：
文献类型：
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作者：
Yu-Chen Zhang;Fei Jiang;Shu‐Liang Wang;F. Shi;S. Tu
苯乙烯的第一个有机催化氧化芳基化是通过邻羟基苯乙烯或对羟基苯乙烯与醌亚胺缩酮的一系列插烯迈克尔加成/烷氧基转移反应建立的。该工艺可实现苯乙烯的高度化学和区域选择性氧芳基化，并以普遍高产率和优异的非对映选择性（高达 99% 的产率，>95:5 dr）获得间烷基化苯胺。对反应途径的研究表明，苯乙烯羟基的存在和位置在级联反应中起着至关重要的作用，这表明联萘衍生的磷酸通过氢键相互作用和长距离共轭效应同时激活两种反应物。此外，产物中羟基官能团的活化基团可以很容易地去除或转化，证明了该策略在苯乙烯氧芳基化和苯乙烯基化合物的合成中的适用性和实用性。
The first organocatalytic oxyarylation of styrenes has been established through a cascade of vinylogous Michael addition/alkoxyl transfer reactions of o- or p-hydroxylstyrenes with quinone imine ketals. The process leads to a highly chemo- and regioselective oxyarylation of styrenes and provides access to m-alkylated anilines in generally high yields and excellent diastereoselectivity (up to 99% yield, >95:5 dr). An investigation of the reaction pathway revealed that the existence and position of the hydroxyl group of styrene played crucial roles in the cascade reaction, suggesting that the two reactants were simultaneously activated by binaphthyl-derived phosphoric acid via hydrogen bonding interactions and long-distance conjugative effects. In addition, the activating group of the hydroxyl functionality in the products can be easily removed or transformed, demonstrating the applicability and utility of this strategy in styrene oxyarylation and in the synthesis of styrene-based compounds.