The insertion of diazo carbene into Si−H bonds with unsupported nanoporous copper (CuNPore) catalyst has been developed. α‐Aryl diazoesters, diazophosphonates, and unstable aryl diazoalkyls can be used as carbene precursors to exquisitely insert into the Si−H bond of silanes. A variety of α‐silylesters, silylphosphonate, and functionalized arylsilane were obtained in 35−82% yields. The reusability feature of the CuNPore catalyst for this insertion reaction demonstrated its high heterogeneous catalytic activity and practicality.Further, mechanistic studies revealed that the insertion of carbene from diazo compounds into the Si−H bond may include a three‐center concerted transition state on CuNPore.

中文翻译：

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无支撑纳米多孔铜催化将 α-重氮化合物中的卡宾插入氢硅烷中


已经开发了将重氮卡宾插入到带有无载体纳米多孔铜 （CuNPore） 催化剂的 Si-H 键中的方法。α-芳基重氮酯、重氮膦酸盐和不稳定的芳基重氮烷基可用作卡宾前驱体，巧妙地插入硅烷的 Si-H 键中。以 35-82% 的收率获得各种 α-甲硅烷酯、甲硅烷基膦酸盐和功能化芳基硅烷。CuNPore 催化剂在这种插入反应中的可重用性证明了其高非均相催化活性和实用性。此外，机理研究表明，重氮化合物中的卡宾插入 Si-H 键可能包括 CuNPore 上的三中心协同过渡态。