While migratory functionalization of alkynes has been recognized as a unique way to access allylic functionalities via π-allyl metal intermediates, hydrofunctionalization of 2-alkynes to afford α-functional olefins has been unexplored. We describe herein the use of a cobalt hydride based system for regioselective migratory hydrofunctionalization of 2-alkynes to furnish α-vinylsilanes and α-vinylgermanes by a mechanistic understanding of the cobalt hydride species on alkyne π-bond migration. The key mechanism of alkyne π-bond migration by [bis(dicyclohexylphosphino)ethane]cobalt hydride is strongly supported by both experimental and computational studies, and the role of each reaction component, such as alkynes and silanes, is elucidated to rationalize the unique α-vinyl selectivity.

中文翻译：

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通过钴催化的 2-炔烃迁移氢官能化区域选择性获得 α-乙烯基硅烷和 α-乙烯基锗烷

虽然炔烃的迁移官能化已被认为是通过 π-烯丙基金属中间体获得烯丙基官能团的独特方式，但尚未探索 2-炔烃的加氢官能​​化以提供 α-官能烯烃。我们在本文中描述了基于氢化钴的系统用于 2-炔烃的区域选择性迁移氢官能化以通过对炔烃 π 键迁移的氢化钴物种的机械理解来提供 α-乙烯基硅烷和 α-乙烯基锗烷的用途。[双（二环己基膦）乙烷]钴氢化物的炔烃 π 键迁移的关键机制得到了实验和计算研究的强烈支持，并且阐明了每个反应组分（如炔烃和硅烷）的作用，以合理化独特的 α -乙烯基选择性。