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Catalytic Chemoselective Sulfimidation with an Electrophilic [CoIII(TAML)]-Nitrene Radical Complex

submitted on 30.07.2020, 15:36 and posted on 31.07.2020, 09:08 by N.P. van Leest, J.I. van der Vlugt, Bas de Bruin
The cobalt species PPh4[CoIII(TAMLred)] is a competent and stable catalyst for the sulfimidation of (aryl)(alkyl)-substituted sulfides with iminoiodinanes reaching turnover numbers up to 900 and turnover frequencies of 640 min-1 under mild and aerobic conditions. The sulfimidation proceeds in a highly chemoselective manner, even in the presence of alkenes or weak C-H bonds, as supported by inter- and intramolecular competition experiments. Functionalization of the sulfide substituent with various electron-donating and electron-withdrawing arenes and several alkyl, benzyl and vinyl fragments is tolerated, with up to quantitative product yields. Sulfimidation of phenyl allyl sulfide led to [2,3]-sigmatropic rearrangement of the initially formed sulfimide species to afford the corresponding N-allyl-S-phenyl-thiohydroxylamines as attractive products. Mechanistic studies suggest that the actual nitrene transfer to the sulfide proceeds via (previously characterized) electrophilic nitrene-radical intermediates that afford the sulfimide products via electronically asynchronous transition states, in which SET from the sulfide to the nitrene-radical complex precedes N-S bond formation in a single concerted process.


The Netherlands Organization for Scientific Research (NWO TOP-Grant 716.015.001 to BdB)

Research Priority Area Sustainable Chemistry of the University of Amsterdam (RPA SusChem, UvA)


Email Address of Submitting Author


University of Amsterdam (UvA)


The Netherlands

ORCID For Submitting Author


Declaration of Conflict of Interest

no conflict of interest

Version Notes

This is version 1.