Stereoselective Synthesis of Z‑Vinylsilanes via Palladium-Catalyzed Direct Intermolecular Silylation of C(sp2)–H Bonds

An efficient and convenient palladium-catalyzed direct intermolecular silylation of C­(sp2)–H bonds by using disilanes as the silicon source with the assistance of a readily removable bidentate directing group is reported. This strategy provided a regio- and stereoselective protocol for exclusive synthesis of Z-vinylsilanes with reasonable to excellent yields and good functional group compatibility. Silylation of the isolated palladacycle intermediate revealed the Z-stereoselective pathway. Moreover, the practicality and effectiveness of this method were illustrated by a gram-scale experiment and further functionalization of the silylation product.本研究报道了一种高效便捷的钯催化分子间直接C(sp²)–H键硅基化反应，以二硅烷作为硅源，在易于脱除的双齿导向基团辅助下完成转化。该策略兼具区域选择性与立体选择性，可专一合成Z-型乙烯基硅烷，反应收率从中等到优秀不等，且具备良好的官能团兼容性。对分离得到的钯环中间体进行硅基化实验，证实该反应遵循Z型立体选择性路径。此外，通过克级规模实验以及硅基化产物的后续官能团转化，验证了该方法的实用性与有效性。