Highly Selective C-N and C-S Dual Functionalization of 1,3-Dicarbonyl Derivatives Using TBHP as an Oxidant.

A direct electrosynthesis/photocatalyst-free, atom-economical, and efficient method for the selective synthesis of ( E )-3-amino-2-thiocyanato-α,β-unsaturated carbonyl compounds is described through a given protocol. The present approach features the use of inexpensive ammonium thiocyanate to achieve dual functionalization of 1,3-dicarbonyl compounds using TBHP as an oxidant, providing a rapid and practical route to the selective formation of both C-N and C-S bonds via a radical process. This method offers a broad substrate scope with excellent yield and allows for further exploration of the products to construct heterocyclic compounds and other functionalities.