Strategies for Direct, Transition Metal‐Free Addition of Nitrogen Synthons to Alkenes

Abstract The incorporation of nitrogen into small molecules is one of the highest‐demanded transformations in modern synthetic chemistry. Alkene difunctionalization and aziridination offer desirable approaches to the incorporation of these amino synthons from feedstock precursors. Although amino groups can be added to alkenes following alkene reaction with an initiation reagent, the most desirable approach involves direct addition of the nitrogen group to the alkene, allowing for a range of possible secondary functionalization outcomes. Although many of these strategies have been accomplished through the use of transition metals, the utility of a transition metal‐free approach is still at the forefront of synthetic chemistry, both in development and demand. This review aims to present a comprehensive review of the history and current state‐of‐the‐art in the transition metal‐free, direct addition of nitrogen to alkenes.