Catalysis and Scope of the Hydroamination of Non‐activated CC Multiple Bonds

Abstract

Amines, enamines, imines, and nitrogen containing heterocycles find manifold commercial uses as bulk chemicals, specialty chemicals, and pharmaceuticals. With the promise of an atom-efficient pathway from readily accessible starting materials, the synthesis of such nitrogen compounds by exploiting the direct formation of CN bonds through the addition of amines to unsaturated CC bonds (hydroamination) is particularly attractive. Many rare-earth and actinide metal complexes are highly efficient catalysts for the intramolecular hydroamination of alkenes, dienes, allenes and alkynes, but reduced rates are observed frequently in intermolecular hydroamination. Attractive features of rare-earth and actinide metal catalysts include very high turnover frequencies and excellent stereoselectivities, rendering this methodology applicable to concise synthesis of naturally occurring alkaloids and other polycyclic azacycles. Recent studies have demonstrated an asymmetric variant of the Bronsted acid catalysis of reactions involving dienes or allenes and achieved high efficiency in intramolecular hydroamination.