AbstractThe synthesis of a broad range of enantioenriched amines by the direct Fe‐catalysed coupling of amines with alcohols through the borrowing hydrogen strategy, while at least one of these substrates is achiral is reported. When starting from α‐chiral amines and achiral alcohols, a wide range of enantioenriched amine products, including N‐heterocyclic moieties can be obtained with complete retention of stereochemistry and the power of this method is demonstrated in the one‐step synthesis of known pharmaceuticals from commercially available, simple enantiopure primary amines and achiral alcohols. It was also found that the use of β‐branched enantioenriched primary alcohols and achiral amines as reaction partners leads to a partial loss of stereochemical integrity in the final product, however, a systematic optimization enabled partial retention of enantiopurity and possible parameters effecting for racemization were identified.magnified image