Copper-catalyzed regioselective double anti-Markovnikov hydrosilylation of terminal alkynes has been developed by employing a copper catalyst generated from readily available CuOAc and 1,3-bis(diphenylphosphino)propane (dppp). A wide range of alkyl- and arylacetylenes undergo this dihydrosilylation reaction to afford gem-disilylalkanes in high isolated yields with high selectivity. Mechanistic studies, including identification and isolation of reactive intermediates, control experiments, deuterium-labeling reactions, and stoichiometric organometallic reactions, reveal that this copper-catalyzed formal dihydrosilylation of terminal alkynes proceeds through a reaction sequence combining C(sp)–H silylation of alkynes to form alkynylsilanes, hydrosilylation of alkynylsilanes to provide gem-disilylalkenes, and hydrogenation of gem-disilylalkenes to afford gem-disilylalkanes. Both copper hydride and copper acetylide species are key active intermediates for this copper-catalyzed dihydrosilylation process.

中文翻译：

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铜催化末端炔烃的形式二氢硅烷化：AC(sp)–H 硅烷化-氢化硅烷化-氢化序列

通过使用由容易获得的 CuOAc 和 1,3-双（二苯基膦）丙烷（dppp）生成的铜催化剂，开发了铜催化末端炔烃的区域选择性双反马尔可夫尼科夫氢化硅烷化。多种烷基乙炔和芳基乙炔经过这种二氢硅烷化反应，以高分离产率和高选择性提供偕二甲硅烷基烷烃。机理研究，包括反应中间体的识别和分离、对照实验、氘标记反应和化学计量有机金属反应，揭示了这种铜催化的末端炔烃的形式二氢硅烷化反应是通过结合炔烃 C(sp)–H 硅烷化反应的反应序列进行的形成炔基硅烷，炔基硅烷氢化硅烷化以提供偕二甲硅烷基烯烃，以及氢化偕二甲硅烷基烯烃以提供偕二甲硅烷基烷烃。氢化铜和乙炔铜都是这种铜催化二氢硅烷化过程的关键活性中间体。