Ano Yusuke, Kawai Natsuki, Chatani Naoto
Department of Applied Chemistry, Faculty of Engineering, Osaka University 2-1 Yamadaoka, Suita Osaka 565-0871 Japan
Center for Atomic and Molecular Technologies, Graduate School of Engineering, Osaka University 2-1 Yamadaoka, Suita Osaka 565-0871 Japan.
Chem Sci. 2021 Aug 14;12(37):12326-12332. doi: 10.1039/d1sc02873a. eCollection 2021 Sep 29.
The palladium-catalyzed 1,1-alkynylbromination of terminal alkenes with a silyl-protected alkynyl bromide is reported. The method tolerates a diverse range of alkenes including vinylarenes, acrylates, and even electronically unbiased alkene derivatives to afford propargylic bromides regioselectively. Mechanistic studies and DFT calculations indicate that the 1,1-alkynylbromination reaction proceeds the migration of the Pd center followed by the formation of a π-allenyl Pd intermediate, leading to the stereoselective reductive elimination of the C(sp)-Br bond at the propargylic positon.
据报道，通过钯催化末端烯烃与硅基保护的炔基溴进行1,1-炔基溴化反应。该方法适用于多种烯烃，包括乙烯基芳烃、丙烯酸酯，甚至电子中性的烯烃衍生物，可区域选择性地得到炔丙基溴。机理研究和密度泛函理论（DFT）计算表明，1,1-炔基溴化反应通过钯中心的迁移，随后形成π-烯丙基钯中间体进行，从而导致在炔丙基位置立体选择性地还原消除C(sp)-Br键。
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