Rhodium-Catalyzed Hydrocarbonylation of a Homoallylamine via N-H Activation and Application for Synthesis of Yohimbane Alkaloids
Rhodium-Catalyzed Hydrocarbonylation of a Homoallylamine via N-H Activation and Application for Synthesis of Yohimbane Alkaloids
复制标题
DOI：
10.1021/om500498u
复制
发表时间：
2014-08-25
期刊：
影响因子：
2.8
通讯作者：
Wu, Chen-Chang
中科院分区：
文献类型：
--
作者：
Chiou, Wen-Hua;Wang, Yu-Wei;Wu, Chen-Chang
我们描述了使用铑催化加氢羰基化合成正育亨烷和别育亨烷，这提供了一个实用的方法来合成从仲高烯丙基胺的δ-内酰胺。我们还观察到一个意想不到的转变，其中胺质子作为氢化物参与加氢羰基化。的D-标记的实验结果和初步DFT计算表明，转换可以合理化的氧化裂解的homoallyl胺的金属氢化物配合物。
We describe syntheses of n-yohimbane and alloyohimbane using Rh-catalyzed hydrocarbonylation, which provides a practical methodology to synthesize a delta-lactam from a secondary homoallyl amine. We have also observed an unexpected transformation where the amine proton served as a hydride to participate in hydrocarbonylation. The D-labeled experimental results and preliminary DFT-calculations suggest that the transformation can be rationalized by oxidative cleavage of the homoallyl amines to a metal hydride complex.