催化 C-H 键锡化反应：通过 C-H 键功能化构建 C-Sn 键的新区域选择性途径。

Catalytic C-H bond stannylation: a new regioselective pathway to C-Sn bonds via C-H bond functionalization.

机构信息

Department of Chemistry & Biochemistry, University of Windsor, Windsor, ON, Canada N9B 3P4.

出版信息

J Am Chem Soc. 2010 Sep 1;132(34):11923-5. doi: 10.1021/ja105588v.

PMID:20690675

Abstract

The ubiquitous Stille coupling reaction utilizes Sn-C bonds and is of great utility to organic chemists. Unlike the B-C bonds used in the Miyaura-Suzuki coupling reaction, which are readily obtained via direct borylation of C-H bonds, routes to organotin compounds via direct C-H bond functionalization are lacking. Here we report that the nickel-catalyzed reaction of fluorinated arenes and pyridines with vinyl stannanes does not provide the expected vinyl compounds via C-F activation but rather provides new Sn-C bonds via C-H functionalization with the loss of ethylene. This mechanism provides a new unanticipated methodology for the direct conversion of C-H bonds to carbon-heteroatom bonds.

摘要

普遍存在的 Stille 偶联反应利用 Sn-C 键，对有机化学家非常有用。与 Miyaura-Suzuki 偶联反应中使用的 B-C 键不同，后者可以通过 C-H 键的直接硼化轻易获得，而通过直接 C-H 键功能化获得有机锡化合物的途径却很少。在这里，我们报告了镍催化的氟化芳烃和吡啶与乙烯基锡烷的反应，该反应不是通过 C-F 活化生成预期的乙烯基化合物，而是通过 C-H 官能化和乙烯的损失生成新的 Sn-C 键。这种机制为直接将 C-H 键转化为碳杂原子键提供了一种新的意外方法。