Diastereoselective C−H Bond Amination for Disubstituted Pyrrolidines

We report herein the improved diastereoselective synthesis of 2,5‐disubstituted pyrrolidines from aliphatic azides. Experimental and theoretical studies of the C−H amination reaction mediated by the iron dipyrrinato complex (AdL)FeCl(OEt2) provided a model for diastereoinduction and allowed for systematic variation of the catalyst to enhance selectivity. Among the iron alkoxide and aryloxide catalysts evaluated, the iron phenoxide complex exhibited superior performance towards the generation of syn 2,5‐disubstituted pyrrolidines with high diastereoselectivity. Iron dipyrrin complexes catalyze the diastereoselective conversion of aliphatic azides into 2,5‐disubstituted pyrrolidines. A combination of experimental and theoretical investigations unveiled the features required for diastereocontrol.