Recent Developments in Selenylation and Thiolation of Alkenes via Three‐component Reactions

Abstract Alkenes are valuable feedstocks in organic synthesis. Selenium or sulfur‐containing coumpounds with a neighboring functional group can be easily prepared by direct difunctionalization of alkenes via three‐component reactions. It will reduce the number of steps and waste generation, and form complicated molecules from simple starting materials. Herein, recent developments (2013–2022) have been summarized via two categories: (1) selenylation via seleniranium intermediates or Se‐centered radicals; (2) thiolation with more diverse mechanisms and products Reactions with electron‐rich arenes, alcohols, water, acids, NaN 3 , amines, KSCN, and sulfamides, TMSNCS, TMSN 3 , Et 3 N ⋅ 3HF, SOCl 2 , HCl, NFSI, t BuONO, pyridinium salts, t BuOOH, ArN 2 BF 4 , CO 2 , CO, O 2 , CF 3 SO 2 Cl, R 2 P(O)−H, (RO) 2 P(O)SH, (RO) 2 P(O)OH et al will be discussed. We hope this review will do help for future research in this area.