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

preprint
submitted on 30.07.2020 and posted on 31.07.2020 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.

Funding

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)

History

Email Address of Submitting Author

b.debruin@uva.nl

Institution

University of Amsterdam (UvA)

Country

The Netherlands

ORCID For Submitting Author

0000-0002-3482-7669

Declaration of Conflict of Interest

no conflict of interest

Version Notes

This is version 1.

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