Indirect ortho functionalization of substituted toluenes through ortho olefination of N,N-dimethylbenzylamines tuned by the acidity of reaction conditions
Indirect ortho functionalization of substituted toluenes through ortho olefination of N,N-dimethylbenzylamines tuned by the acidity of reaction conditions
复制标题
DOI：
10.1021/ja070588a
复制
发表时间：
2007-06-20
影响因子：
15
通讯作者：
Shi, Zhangjie
中科院分区：
文献类型：
--
作者：
Cai, Guixin;Fu, Ye;Shi, Zhangjie
在分析取代N，N-二甲基苄胺烯化反应特点的基础上，通过调节反应条件的酸度，发展了高区域选择性的烯化反应。邻位官能化的N，N-二甲基苄胺在温和条件下进一步转化为3-（2 ′-甲苯基）丙酸及其衍生物。这两种转化可以合并到一锅中，并且以中等至良好的产率获得3-（2 '-甲苯基）丙酸及其衍生物。机理研究表明，亲电攻击的苯环上的Pd（II）离子辅助的N，N-二甲基氨基甲基是一个关键步骤，在此催化转化，这是由反应条件的酸度控制。
Highly regioselective olefination of substituted N,N-dimethylbenzylamines was developed by tuning the acidity of reaction conditions based on analysis of their features. The ortho-functionalized N,N-dimethylbenzylamines were further transformed into 3-(2'-tolyl)propanoic acid and its derivatives under mild conditions. These two transformations could be combined into one pot, and 3-(2'-tolyl)propanoic acid and its derivatives were obtained in moderate to good yields. Mechanistic studies indicated that electrophilic attack on the phenyl ring by the Pd(II) ion assisted by the N,N-dimethylaminomethyl group was a key step during this catalytic transformation, which was controlled by the acidity of the reaction conditions.