Electrophilic Thiocyanato Reagent Assisted Oxa-Michael/Thiocyanation of α,ß-Unsaturated Ketones.

A route for thiocyanation-functionalization of the electron-deficient C═C double bond was developed. Regioselective thiocyanation-etherification of α,ß-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.

Rhodium(III)-Catalyzed Oxidative Cross-Coupling of N-Pyrimidylindoles with Cyclic ß-Keto Esters for Accessing All-Carbon Quaternary Centers.

Rh(III)-catalyzed direct oxidative C-H/C-H cross-coupling between N-pyrimidylindoles and ß-ketoesters is presented. Easily available ß-ketoesters are used as an alkylating agent for the facile construction of all-carbon quaternary centers under mild conditions. The ester group in the product can undergo decarboxylation or decarboxylative amination.