Stereoselective Cope-Type Hydroamination of Allylic Amines Using Simple Aldehydes as Catalysts

Abstract

Stereoselective hydroaminations of unactivated alkenes are rare as this represents a very challenging synthetic transformation. The most efficient examples occur in biased intramolecular systems and highly enantioselective intermolecular examples are rare, which is consistent with the forcing conditions required to catalyze the reactions. This limited reactivity also accounts for the lack of highly diastereoselective hydroamination variants. Recently our group has shown that intermolecular Cope-Type hydroamination of unactivated alkenes can be achieved using simple aldehydes as catalysts. The aldehyde promotes pre-association of the two reaction partners, inducing temporary intramolecularity resulting in a remarkably facile hydroamination event. This thesis will present the development of two reactions: intermolecular enantioselective Cope-type hydroamination and intermolecular diastereoselective Cope-type hydroamination of allylic amines.