Effective Formylation of Amines with Carbon Dioxide and Diphenylsilane Catalyzed by Chelating bis( tz NHC) Rhodium Complexes

The reductive formylation of amines using CO 2 and hydrosilanes is an attractive method for incorporating CO 2 into valuable organic compounds. However, previous systems required either high catalyst loadings or high temperatures to achieve high efficiency, and the substrate scope was mostly limited to simple amines. To address these problems, a series of alkyl bridged chelating bis(NHC) rhodium complexes (NHC=N‐heterocyclic carbene) have been synthesized and applied to the reductive formylation of amines using CO 2 and Ph 2 SiH 2 . A rhodium‐based bis( tz NHC) complex ( tz =1,2,3‐triazol‐5‐ylidene) was identified to be highly effective at a low catalyst loading and ambient temperature, and a wide substrate scope, including amines with reducible functional groups, were compatible.