A route for thiocyanation-functionalization of the electron-deficient CC double bond was developed. Regioselective thiocyanation-etherification of α,β-unsaturated ketones was achieved. The desired products were obtained in moderate to high yields under mild conditions. It was suggested that the nucleophile was activated by the electrophilic thiocyanato reagent, and difunctionalization was achieved through a 1,4-addition/thiocyanation pathway.

A new thiocyanation/cyclization reaction was developed to synthesize thiocyanato-containing oxygen heterocyclic compounds with terminal and non-terminal enols. The approach supplies an efficient method to build the multi-substituted ring and spiro ring structure of furan, which has a wide range of substrates, good functional group tolerance, and the desired products can be obtained in a medium to high yield.

An efficient bifunctional cinchona alkaloids‐catalyzed asymmetric tandem intramolecular oxa‐Michael addition/electrophilic thiocyanation of alkylidene β‐ketoesters with N‐thiocyanatosuccinimide (NTS) was developed. A series of chiral α‐thiocyanato flavanones containing two vicinal stereocenters including an all‐carbon quaternary center were prepared in good yields with excellent diastereo‐ and enantioselectivities (up to 97% ee) under mild conditions, and a successful scale up preparation of our protocol was also demonstrated.