Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters

Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl](2) (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.

Automated summary

The decarbonylative synthesis of thioethers from thioesters catalyzed by Rh is reported, showing excellent group tolerance to aryl chlorides and bromides without the need for phosphine ligands or inorganic bases. The methodology allows for gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage.