The Azidofunctionalization of Alkenes

Abstract

The azidofunctionalization of alkenes has emerged as a powerful difunctionalization strategy, expanding the toolbox of synthetic chemistry. This transformation enables the simultaneous installation of an azide and a second functional group onto an alkene, facilitating access to diverse nitrogen-containing compounds. The azidofunctionalization is particularly valuable in pharmaceutical and materials chemistry, as azides serve as key intermediates in the synthesis of bioactive molecules and polymers. Various catalytic and radical-mediated approaches are developed. Photoredox catalysis, transition metal-mediated reactions, and hypervalent iodine chemistry have enabled regio- and stereoselective transformations under mild conditions. Radical-mediated methods, in particular, provide high efficiency and broad substrate scope, enabling the incorporation of azide groups even in complex molecular scaffolds. Recent advances have also explored enantioselective azidofunctionalization using chiral catalysts, opening new opportunities for the asymmetric synthesis of nitrogen-containing derivatives. This review provides a comprehensive overview of azidofunctionalization methodologies, highlighting the diverse functional groups that have been introduced in a single-step alongside an azide.