Trifluoromethylthiolation-Based Bifunctionalization of Diazocarbonyl Compounds by Rhodium Catalysis.

A new Rh-catalyzed, three-component reaction for the oxytrifluoromethylthiolation of α-diazoketones was developed. The SCF3 functionality was introduced using a stable dibenzenesulfonimide reagent under mild conditions. Alcohols, acetals, and ethers were used as the alkoxy sources. Cyclic ethers underwent a trifunctionalization reaction through the introduction of SCF3, OR, and N(SO2Ph)2 substituents in a single step.