The preparation of N-tert-butyloxycarbonyl-(Boc-)protected sulfoximines and sulfimines by an iron(II)-mediated nitrene transfer from BocN3 to sulfoxides and sulfides

Thorsten Bach, Christina Körber

Publikation: Beitrag in FachzeitschriftArtikelBegutachtung

119 Zitate (Scopus)

Abstract

The imidation of sulfides and sulfoxides to the corresponding sulfimides and sulfoximides was carried out with N-tert-butyloxycarbonyl azide (BocN3) in the presence of FeCl2. Sulfoxides 1 reacted at room temperature in CH2Cl2 to give the corresponding sulfoximides 3 in 40-95% yield. The imidation of the sterically congested substrate tert-butyl methyl sulfoxide (1f) proceeded sluggishly (10% yield). The sterospecificity of the reaction was demonstrated with the enantiomerically enriched substrates (R)-(+)-1b and (S)-(-)1d which yielded the sulfoximides (R)-(+)-3b and (S)-(-)-3d with retention of configuration. Mechanistically, an intermediate (nitrene)Fe(IV) complex is postulated as the reactive nitrene transfer reagent which is formed from FeCl2 and BocN3. The more nucleophilic sulfides 2 reacted more readily in the imidation than sulfoxides. Their conversion to the corresponding sulfimides 4 was conducted with BocN3 and a substoichiometric amount of FeCl2 (0.25 equiv.). Yields ranged between 44 and 92%. In an alternative reaction mode, BocN3 was utilized at 0°C in the presence of FeCl2 and acetyl acetone. The sulfimidation, which did not otherwise occur at this temperature, was accelerated by the ligand (36-90% yield).

OriginalspracheEnglisch
Seiten (von - bis)1033-1039
Seitenumfang7
FachzeitschriftEuropean Journal of Organic Chemistry
Ausgabenummer5
DOIs
PublikationsstatusVeröffentlicht - Mai 1999
Extern publiziertJa

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