Unsupported Nanoporous Copper Catalyzed Insertion of Carbenes from α‐Diazo Compounds into Hydrosilanes

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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.