Xu Yanli, Hu Weigao, Tang Xiaodong, Zhao Jinwu, Wu Wanqing, Jiang Huanfeng
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, China.
Chem Commun (Camb). 2015 Apr 21;51(31):6843-6. doi: 10.1039/c5cc01661d.
A highly selective palladium-catalyzed carbonylation of Csp(2)-H bonds with aromatic oximes for the synthesis of benzo[d][1,2]oxazin-1-ones and 3-methyleneisoindolin-1-ones has been developed. Interestingly, we found that the N-OH group of the oximes could be used as a directing group and/or an internal oxidant under different conditions. This transformation is supposed to proceed through a hydroxyl-directed ortho-Csp(2)-H carbonylation or activation of vinyl Csp(2)-H bond/ortho-Csp(2)-H carbonylation process. The uses of readily available starting materials, atmospheric pressure of carbon monoxide, as well as operational simplicity make this practical and atom-economical method particularly attractive.
已开发出一种高度选择性的钯催化的Csp(2)-H键与芳基肟的羰基化反应，用于合成苯并[d][1,2]恶嗪-1-酮和3-亚甲基异吲哚-1-酮。有趣的是，我们发现肟的N-OH基团在不同条件下可作为导向基团和/或内氧化剂。这种转化被认为是通过羟基导向的邻位Csp(2)-H羰基化或乙烯基Csp(2)-H键的活化/邻位Csp(2)-H羰基化过程进行的。使用容易获得的起始原料、一氧化碳的常压以及操作简便使得这种实用且原子经济的方法特别有吸引力。
