7.19 Addition Reactions with Formation of Carbon[sbnd]Nitrogen Bonds

Abstract

Alkenes are useful starting materials for the synthesis of substituted amines and nitrogen heterocycles through oxidative difunctionalization reactions. Tremendous progress has been made in this field in the past two decades with the emergence of several transition metal complexes and organocatalysts that are able to mediate these reactions. This chapter highlights the main achievements made since the review by Kemp published in the first edition of Comprehensive Organic Synthesis. Attention is successively paid to aziridination, oxyamination, diamination, aminohalogenation, and carboamination of alkenes. The main reagents and catalysts are described for each reaction and this survey demonstrates the impact of palladium, copper, and dirhodium complexes, as well as the growing influence of iodine(III) oxidants. Mechanisms are also provided for key transformations. Their synthetic utility is then showcased by relevant applications in natural product synthesis or medicinal chemistry.