One-Pot Alkene Hydroboration/Palladium-Catalyzed Migratory Suzuki-Miyaura Cross-Coupling
One-Pot Alkene Hydroboration/Palladium-Catalyzed Migratory Suzuki-Miyaura Cross-Coupling
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DOI：
10.1021/acscatal.0c02755
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发表时间：
2020-09-18
期刊：
影响因子：
12.9
通讯作者：
Baudoin, Olivier
中科院分区：
文献类型：
--
作者：
Baumgartner, Yann;Baudoin, Olivier
链行走是一种强有力的功能化的C-H键远程功能基团的方法。尽管在过去几年中已经开发了各种Pd催化的迁移交叉偶联，但流行的Suzuki-Miyaura交叉偶联的有效迁移版本的设计仍然难以捉摸。本文报道了一种由烯烃硼氢化和迁移Suzuki-Miyaura偶联得到的烷基硼酸中间体组成的一锅法。以P（t-Bu）（2）Me为配体，邻位取代芳基为亲电试剂，对起始烯烃的苄基位置具有较高的区域选择性.从烯烃的位置和几何异构体的区域收敛和远程迁移证明。机制研究表明，迁移发生通过一个部分可逆的，非解离机制。
Chain-walking is a powerful approach toward the functionalization of C-H bonds remote to a functional group. Whereas various Pd-catalyzed migratory cross-couplings have been developed in the past years, the design of an efficient migratory version of the popular Suzuki-Miyaura cross-coupling has remained elusive. The current article reports a one-pot procedure consisting of alkene hydroboration and migratory Suzuki-Miyaura coupling of the resulting alkylboronic acid intermediate. A high regioselectivity for the benzylic position of the initial alkene was achieved by using P(t-Bu)(2)Me as the ligand and an ortho-substituted aryl electrophile. Regioconvergence from alkene positional and geometrical isomers and long-range migration were demonstrated. Mechanistic investigations indicated that the migration occurs through a partially reversible, nondissociative mechanism.