Electrochemically Driven Hydroxy‐Thiocarbamation of Electron‐Deficient Alkenes

This article reports the first example of multi‐component hydroxy‐thiocarbamation of electron‐deficient alkenes in an electrochemical undivided cell. Simple and readily available electron‐deficient (hetero)aryl alkenes, KSCN and H 2 O are used as starting materials to produce β‐hydroxy primary S‐thiocarbamate derivatives in moderate to good yields. H 2 O is involved in the formation of carbamoyl and hydroxyl groups, making the method highly atom‐economical. The reaction introduces multiple functional groups under mild and environmentally friendly conditions, without the need for metals or external oxidants. The reaction exhibits good functional‐group tolerance and excellent product diversity. The procedure is operationally simple, and late‐stage modification of natural products further demonstrates the practical application of the method.