Synergistic Radical Markovnikov Hydroselenization of Alkenes

Abstract Herein, we report a new synergistic radical Markovnikov hydroselenization of alkenes by in‐situ generated selenium cluster that absorbs hydride under mild conditions. In this protocol, a formal “metal hydride” mechanism is proposed, in which the hydrogen atom is added into the alkene, then undergoing S H 2 radical substitution to give the dialkyl selenides products that previously are inaccessible. This metal‐free double selenium‐ene reaction enables smoothly the installation of the bioactive Se atom into a remarkably wide scope of aliphatic and aromatic alkenes and pharmaceuticals‐derived alkenes along with high functional groups compatibility.