Highly efficient and chemoselective oxidation of sulfides catalyzed by iron(III) corroles with iodobenzene diacetate

• We report an efficient iron corrole-catalyzed sulfoxidation using iodobenzene diacetate.
• We screen the reaction conditions and scope, and demonstrate the synthetic utility.
• We conduct Hammett correlation and spectra studies to probe the active intermediate.
• We propose a high-valent iron(V)-oxo intermediate as the active oxidant.

Iron(III) corrole complexes catalyze the highly chemoselective oxidation of sulfides to sulfoxides with iodobenzene diacetate [PhI(OAc)2] as a mild oxygen source. Various substituted thioanisoles, vinyl sulfides, and hydroxyl sulfides can be efficiently oxidized to sulfoxides with quantitative conversions (up to 5000 TONs) and excellent selectivities without over-oxidation to sulfones. The remarkably enhanced catalytic activity and stability against degradation is ascribed to the slow and steady-state formation of PhIO from highly soluble PhI(OAc)2 in the presence of a small amount of water. On the basis of Hammett correlation and mixing UV–vis spectral studies, a putative high-valent iron(V)-oxo species is likely generated as a short-lived active intermediate.

Iron(III) corroles catalyze highly efficient and chemoselective sulfoxidations with iodobenzene diacetate as the promising oxygen source. Various substituted thioanisoles, vinyl sulfides, and hydroxyl sulfides can be efficiently oxidized to sulfoxides with quantitative conversions and excellent chemoselectivies.Figure optionsDownload as PowerPoint slide