Mechanistic Insights on a Metal-Free Borylative Cyclization of Alkynes Using BCl3: A Theoretical Investigation
Mechanistic Insights on a Metal-Free Borylative Cyclization of Alkynes Using BCl3: A Theoretical Investigation
复制标题
使用 BCl3 进行炔烃无金属硼化环化的机理见解：理论研究
DOI：
10.1002/ajoc.201700343
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发表时间：
2017-11-01
影响因子：
2.7
通讯作者：
Xu, Liang
中科院分区：
文献类型：
--
作者：
Wei, Yu;Liu, Dongwei;Xu, Liang
The metal-free reactions between alkynes and BCl3 were investigated by means of DFT calculations, focusing on elucidating the detailed cyclization mechanism and the different chemoselectivity between internal and terminal alkynes. The results showed that borylative cyclization of internal alkynes proceeded via kinetically favorable stepwise complexation, electrophilic dearomatization, hydrogen migration and rearomatization. In contrast, for terminal alkynes, the competitive chloroboration step, which followed the complexation step, was more feasible than electrophilic dearomatization, affording the thermodynamically stable addition products irreversibly.
