Efficient and Highly Chemoselective Direct Reductive Amination of Aldehydes using the System Silane/Oxorhenium Complexes

This work reports a novel method for direct reductive amination of aldehydes with silanes catalyzed by several high‐valent oxorhenium(V) and oxorhenium(VII) complexes. The catalytic system PhSiH3/ReIO2(PPh3)2 (2.5 mol%) was very efficient for the synthesis of secondary amines and highly chemoselective, tolerating a wide range of functional groups such as NO2, CF3, SO2R, CO2R, F, Cl, Br, I, CN, OH, OCH3, SCH3, NCOR, and double bonds. This novel method was also employed in the synthesis of tertiary amines with moderate yields.