Iron(II)-Catalyzed Nitrene Transfer Reaction of Sulfoxides with N-Acyloxyamides

Abstract

An iron(II)-catalyzed nitrene transfer reaction of sulfoxides with N-acyloxyamides has been developed, leading to the efficient construction of N-acyl sulfoximines with high functional-group compatibility. The current catalytic transformation was carried out under an air atmosphere at ambient temperature and could be scaled up to gram scale with a catalyst loading of 1 mol %. Application of the methodology was demonstrated by facile C−H acetoxylation and olefination using the N-acyl sulfoximine as the directing group.

Nitrene transfer reaction with hydroxylamine derivatives

“…Subsequently, an iron(II)-catalysed nitrene transfer to sulfoxides with N-acyloxyamides was developed, leading to the efficient construction of N-acyl sulfoximines with high functional group compatibility (Scheme 31b). 59 In addition, their group achieved a facile imidization of phosphines with N-acyloxyamides by using FeCl 2 as the catalyst (Scheme 31c). 60 Lebel et al documented a diastereoselective amination of thioethers with chiral N-mesyloxycarbamate S-14 for the synthesis of chiral sulfilimines (Scheme 32).…”

One-Pot Tandem Oxidative Bromination and Amination of Sulfenamide for the Synthesis of Sulfinamidines

“…In the past few years, the synthesis of sulfur derivatives has received great attention from academic research groups and pharmaceutical companies alike . Sulfone, sulfonamide, and sulfonic ester are well-established S­(VI) functionalities that feature in most sulfur-containing FDA-approved drugs, and recently, their aza analogues such as sulfoximine, ,, sulfonimidamide, and sulfonimidate ester have been growing interest in the development of synthetic methodologies . Replacement of one of the oxygen atoms with nitrogen provides favorable stability and solubility, multiple hydrogen-bond acceptor/donor functionalities, and structural diversity. , However, sulfinamidines, the monoaza analogues of sulfinamides, received limited attention from both organic chemists and pharmaceutical chemists.…”

Condition-Controlled O-Acylation and N–O Bond Reduction of Hydroximic Acids with Thioacetic Acid

“…Furthermore, thioacetic acid could serve as a reducing reagent for the deoxygenation of sulfoxides and the reduction of azides and azobenzenes . On the basis of our previous research interests in the novel transformations of amide scaffolds, we postulated that the hydroxamic acid could undergo O -acylation with thioacetic acid to deliver the N -acyloxy amide, which has a lower N–O BDE. Then, in a cascade process, thioacetic acid serves as a reducing agent, enabling the N–O bond cleavage of the N -acyloxy amide intermediate to afford the primary amide as the final product [Scheme -(3)].…”