Chen Qing-An, Chen Zhiwei, Dong Vy M
Department of Chemistry, University of California, Irvine, 4403 Natural Sciences 1, Irvine, California 92697, United States.
J Am Chem Soc. 2015 Jul 8;137(26):8392-5. doi: 10.1021/jacs.5b05200. Epub 2015 Jun 29.
The hydroamination of internal alkynes via tandem rhodium catalysis gives branched N-allylic indolines with high regio- and enantioselectivity. An acid switch provides access to the linear isomer in preference to the branched isomer by an isomerization mechanism. Mechanistic studies suggest formation of an allene intermediate, which undergoes hydroamination to generate allylic amines instead of the enamine or imine products typically observed in alkyne hydroaminations.
通过串联铑催化实现的内炔烃氢胺化反应能够以高区域选择性和对映选择性生成支链N-烯丙基吲哚啉。通过酸转换,可通过异构化机制优先获得线性异构体而非支链异构体。机理研究表明会形成联烯中间体,该中间体进行氢胺化反应生成烯丙基胺,而非炔烃氢胺化反应中通常观察到的烯胺或亚胺产物。