A highly stereoselective synthesis of thiocyanated enaminones was achieved by an electrochemical process, which involved C–H bond thiocyanation and vinyl C–N bond transamination.

The transmetalation as the rate-limiting step was effectively accelerated by newly designed N-heterocyclic carbenes with triazine wingtips (T-NHC).

An electrochemical oxidative C(sp 2)-H sulfuration has been developed. Various enaminones and thiophenols were compatible, generating the desired alkenyl sulfur compounds in up to 87 % yield. This transformation proceeded smoothly under mild reaction conditions without external oxidant and transition-metal catalyst. Remarkably, thiophenols selectively coupled with enamines when substrates had other alkenyl groups. In addition, the desired products could be further transformed into a series of αsulfur isoxazoles, which are a kind of useful heterocycles in materials and bioactive molecules.

The benzodiazepines are essential structural motifs commonly found in biologically active compounds and pharmaceutical agents. The general and step-economy methods for the direct synthesis of the benzodiazepines from simple and...