42397-44-4

Upstream product

• 100-68-5 methyl-phenyl-thioether 
• 19226-36-9 3-phenyl-5H-1,4,2-dioxazol-5-one 
• 495-18-1 Benzohydroxamic acid 
• 61650-22-4 N-(pivaloyloxy)benzamide 

Downstream Products

• 54090-90-3 N-(methyl(oxo)(phenyl)-λ⁶-sulfanylidene)benzamide 

Relevant academic research and scientific papers

Synthesis of sulfimides and N-Allyl-N-(thio)amides by Ru(II)catalyzed nitrene transfer reactions of N-acyloxyamides

The N-acyloxyamides were employed as effective N-acyl nitrene precursors in reactions with thioethers under the catalysis of a commercially available Ru(II) complex, from which a variety of sulfimides were synthesized efficiently and mildly. If an allyl group is contained in the thioether precursor, the [2,3]-sigmatropic rearrangement of the sulfimide occurs simultaneously and the N-allyl-N-(thio)amides were obtained as the final products. Preliminary mechanistic studies indicated that the Ru-nitrenoid species should be a key intermediate in the transformation.

Interweaving Visible-Light and Iron Catalysis for Nitrene Formation and Transformation with Dioxazolones

Herein, visible-light-driven iron-catalyzed nitrene transfer reactions with dioxazolones for intermolecular C(sp3)-N, N=S, and N=P bond formation are described. These reactions occur with exogenous-ligand-free process and feature satisfactory to excellent yields (up to 99 %), an ample substrate scope (109 examples) under mild reaction conditions. In contrast to intramolecular C?H amidations strategies, an intermolecular regioselective C?H amidation via visible-light-induced nitrene transfer reactions is devised. Mechanistic studies indicate that the reaction proceeds via a radical pathway. Computational studies show that the decarboxylation of dioxazolone depends on the conversion of ground sextet state dioxazolone-bounding iron species to quartet spin state via visible-light irradiation.

Method for synthesizing N-substituted sulfimide compounds

The invention discloses a method for synthesizing N-substituted sulfimide compounds. The preparation method comprises the following steps: in an air atmosphere, taking N-(hydrocarbon acyloxy) amide and disubstituted thioether as raw materials, taking a ruthenium complex as a catalyst, reacting in a reaction solvent in the presence of a silver salt additive and a ligand, and after the reaction is finished, separating and purifying to obtain the N-substituted sulfimide compounds. The method has the beneficial effects that (1) through comprehensive screening and cooperation of a proper substrate,temperature, the catalyst and the ligand, the application range of the substrate is wide; and (2) compared with the existing method, the method has the advantages of simple raw material synthesis, mild reaction conditions, no need of inert gas protection, simple operation and high reaction efficiency.

Ruthenium-catalyzed asymmetric n-acyl nitrene transfer reaction: Imidation of sulfide

The asymmetric nitrene transfer reaction is a useful and strong tool for the construction of nitrogen functional groups such as N-sulfonyl amide and carbamic ester in a highly enantioselective manner. On the other hand, there is a substantial limitation in this filed: the transfer of N-acyl amide via the corresponding nitrene intermediates is still difficult because N-acyl nitrenes undergo undesired nitrene dimerization or Curtius rearrangement. Herein, we achieved highly enantioselective imidation of sulfides via catalytic N-acyl nitrene transfer with (OC)ruthenium-salen complex 2b as the catalyst and 3-substituted 1,4,2-dioxazol-5-ones 1 as the nitrene source. Complex 2b can decompose dioxazolones 1 to the desired N-acyl nitrene intermediates without any activation via heating or UV irradiation, or transfer generating nitrene intermediates to the sulfur atom of sulfides with good to excellent enantioselectivities (≤98% ee) without diazene and isocyanate contamination.

Sulfur imidations by light-induced ruthenium-catalyzed nitrene transfer reactions

N-Acyl nitrenes have been generated from a range of heterocyclic precursors, and their applications in light-induced ruthenium-catalyzed sulfur imidations have been studied. Analyzing the reaction scope and determining the structural requirements of the in situ formed electrophilic nitrogen species for effective nitrene transfer allowed a mechanistic scheme to be proposed. The mechanistic conclusions were substantiated by the identification of potential intermediates.

Light-induced ruthenium-catalyzed nitrene transfer reactions: A photochemical approach towards N-Acyl sulfimides and sulfoximines

1,4,2-Dioxazol-5-ones are five-membered heterocycles known to decarboxylate under thermal or photochemical conditions, thus yielding N-acyl nitrenes. Described herein is a light-induced ruthenium-catalyzed N-acyl nitrene transfer to sulfides and sulfoxides by decarboxylation of 1,4,2-dioxazol-5-ones at room temperature, thus providing direct access to N-acyl sulfimides and sulfoximines under mild reaction conditions. In addition, a one-pot sulfur imidation/oxidation sequence catalyzed by a single ruthenium complex is reported. Double duty: A one-pot sulfur imidation/oxidation sequence using a single ruthenium complex for both steps was developed (see scheme). Photochemical decarboxylations of 1,4,2-dioxazol-5-ones provide N-acyl nitrenes, which imidate sulfides at ambient temperature. The subsequent oxidation then occurs under mild phase-transfer catalysis conditions. In this manner, N-acyl sulfimides and sulfoximines can be obtained in high yields starting from sulfides.