Insights into Alkene Hydroselenation

Selective hydrofunctionalization of alkenes enables the efficient construction of structurally diverse and value‐added molecules with new functionalities. The past few decades have witnessed rapid applications of organoselenium compounds in pharmaceuticals, pesticides, and materials. Alkene hydroselenation represents one of the most promising strategies for the highly regio‐, chemo‐, and stereoselective synthesis of selenium‐containing substances. This review outlines the hydroselenation reactions of alkenes with selenols or their surrogates developed over the past five decades and discusses the origin of selectivity based on representative examples. These developments are categorized according to the reactivity patterns exhibited by the selenium nucleophiles. Transition metal‐catalyzed, light‐induced, and electrocatalytic hydroselenation are highlighted to enhance the understanding of the mechanism.