Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
Han Cao, Xuejing Liu, Fusheng Bie, Yijun Shi, Ying Han, Peng Yan, Michal Szostak, Chengwei Liu
Abstract
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.
Topics & Concepts
DecarbonylationPhosphineChemistryCatalysisArylIntramolecular forceMedicinal chemistryDerivatizationYield (engineering)Bond cleavageOrganic chemistryAlkylHigh-performance liquid chromatographyMaterials scienceMetallurgySulfur-Based Synthesis TechniquesChemical Synthesis and ReactionsCatalytic C–H Functionalization Methods