Synthesis of Air‐ and Moisture‐Stable,Storable Chiral Oxorhenium Complexes and Their Application as Catalysts for the Enantioselective Imine Reduction

Air‐/moisture‐stable, crystalline, and storable chiral salicyloxazoline based oxorhenium(V) complexes have been synthesized and their catalytic application for the asymmetric reduction of ketimines using hydrosilane as hydride source is disclosed. A broad substrate scope, high yields, and excellent enantioselectivities (up to 99 %) are attained. Furthermore, the syntheses of enantiopure α‐amino esters, γ‐ and δ‐lactams, and isoindolinones have also been carried out using this methodology. Finally, the method has been applied to synthetic targets of pharmaceutical relevance, such as R‐(+)‐salsolidine and R‐(+)‐crispine A.