Synergistic Radical Markovnikov Hydroselenization of Alkenes

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 SH2 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.