Transition metal-catalyzed asymmetric hydroamination of alkenes (AHA)

The hydroamination of unsaturated carbon-carbon linkages allows a facile and highly atom-economical access to industrially relevant nitrogen-containing basic and fine chemicals as well as naturally occurring alkaloid skeletons. Significant research efforts have led to the development of efficient catalyst systems for intra- and intermolecular hydroamination reactions. Of particular interest are hydroaminations promoted by chiral catalysts, in which a new chiral center is generated or chiral substrates are kinetically resolved. This review will give an overview on the current state of the art in this rapidly evolving field of catalysis. 1 Introduction 2 Rare Earth Metal-Based Catalysts 2.1 Hydroamination/Cyclization of Aminoalkenes 2.2 Kinetic Resolution of Chiral Aminoalkenes 3 Group 4 Metal-Based Catalysts 4 Late Transition Metal-Catalyzed Hydroarnination 4.1 Iridium-Based Catalysts 4.2 Palladium- Catalyzed Hydroarnination of Vinylarenes and 1,3-Dienes 4.3 Palladium -Catalyzed Asymmetric Intramolecular Hydroamination of Aminoalkynes 4.4 Asymmetric Aza-Michael Addition of Amines to alpha,beta-Unsaturated Amides and Nitriles 5 Outlook.