24702-26-9

Upstream product

• 623-13-2 4-methylphenyl methylsulfide 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 127-65-1 chloroamine-T 
• 242461-31-0 [N-(p-toluenesulfonyl)imino](2-tert-butylsulfonyl)phenyliodinane 
• 934-72-5 Methyl p-tolyl sulfoxide 
• 40560-76-7 tosyl azide 
• 5056-07-5 (S)-methyl p-tolyl sulfoxide 
• 4104-47-6 N-sulfinyl-p-toluenesulfonamide 
• 144-86-5 N-chloro-4-methylbenzenesulfonamide 
• 10486-08-5 sodium p-thiocresolate 
• 64693-05-6 (RS)-Dimethyl-(1-methylpropyl)-sulfonium-4-methylbenzolsulfonat 
• 106-45-6 para-thiocresol 
• 103-19-5 di(p-tolyl) disulfide 
• 4547-64-2 4-methoxybenzenesulfonyl azide 

Downstream Products

• 623-13-2 4-methylphenyl methylsulfide 
• 28832-82-8 S-methyl-S-p-tolyl-N-(p-tolylsulfonyl)sulfoximine 
• 70-55-3 toluene-4-sulfonamide 
• 96-09-3 styrene oxide 
• 20520-50-7 (R)-S-methyl-S-(4-tolyl)-N-(p-tolylsulfonyl)sulfoximine 
• 20414-85-1 S-methyl-S-(p-tolyl)sulfoximine 
• 58044-92-1 S-methyl-S-(4-tolyl)sulfilimine 
• 20780-53-4 (R)-Styrene oxide 
• 20780-54-5 (S)-styrene oxide 
• 140687-75-8 2-(3,4-dimethoxyphenyl)oxirane 

Relevant academic research and scientific papers

Can chloramine-T be a nitrene transfer agent?

Reaction of chloramine-T and methyl p-tolyl sulfide to give the corresponding sulfimide appears to proceed via a nitrene transfer mechanism in the presence of a copper(I) catalyst and a second nitrogen ligand.

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

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.

Sulfonylimino group transfer reaction using imino-λ3-iodanes with I2 as catalyst under metal-free conditions

A new practical procedure of imination for sulfide has been developed. The treatment of (N-tosylimino)-phenyl-λ3-iodane, PhINTs, with various sulfides in the presence of a catalytic amount of I2 under metal-free conditions affords the corresponding N-tosylsulfilimine compounds with moderate to good yields. This facile transfer procedure of the sulfonylimino group can also be applied to triphenylphosphine to produce the respective iminotriphenylphosphoranes in high yields. According to the reaction mechanism studies, the process of imination from (N-tosylimino)-phenyl-λ3-iodane to sulfide under the conditions may involve radical steps within the reaction mechanism.

Octahedral iron(iv)-tosylimido complexes exhibiting single electron-oxidation reactivity

High valent iron species are very reactive molecules involved in oxidation reactions of relevance to biology and chemical synthesis. Herein we describe iron(iv)-tosylimido complexes [FeIV(NTs)(MePy2tacn)](OTf)2 (1(IV)

Tripodal S-Ligand Complexes of Copper(I) as Catalysts for Alkene Aziridination, Sulfide Sulfimidation, and C-H Amination

Copper(I) complexes of tris(thioimidazolyl)borates (R′TmR), including [Cu(TmPh)(PR″3)] (R″ = Ph, Cu1; Cy, Cu2) and [Cu(R′TmPh)(PR″3)]+ (R′ = N-methylimidazole; R″ = Ph, Cy) were prepared an

A Mononuclear Nonheme Iron(V)-Imido Complex

Mononuclear nonheme iron(V)-oxo complexes have been reported previously. Herein, we report the first example of a mononuclear nonheme iron(V)-imido complex bearing a tetraamido macrocyclic ligand (TAML), [(TAML)FeV(NTs)]? (1). The spectroscopic characterization of 1 revealed an S = 1/2 Fe(V) oxidation state, an Fe - N bond length of 1.65(4) ?, and an Fe - N vibration at 817 cm-1. The reactivity of 1 was demonstrated in C - H bond functionalization and nitrene transfer reactions.

Methods and systems for sulfimidation or sulfoximidation of organic molecules

The disclosure generally relates to the fields of synthetic organic chemistry. In particular, the present disclosure relates to methods and systems for the imidation of sulfides.

A diiron(III,IV) imido species very active in nitrene-transfer reactions

Metal-catalyzed nitrene transfer reactions arouse intense interest as clean and efficient procedures for amine synthesis. Efficient Rh- and Ru-based catalysts exist but Fe alternatives are actively pursued. However, reactive iron imido species can be very short-lived and getting evidence of their occurrence in efficient nitrene-transfer reactions is an important challenge. We recently reported that a diiron(III,II) complex is a very efficient nitrene-transfer catalyst to various substrates. We describe herein how, by combining desorption electrospray ionization mass spectrometry, quantitative chemical quench experiments, and DFT calculations, we obtained conclusive evidence for the occurrence of an {FeIIIFeIV=NTosyl} intermediate that is very active in H-abstraction and nitrene-transfer reactions. DFT calculations revealed a strong radical character of the tosyl nitrogen atom in very low-lying electronic configurations of the FeIV ion which are likely to confer its high reactivity. Nitrene transfer: An FeIIIFeIV imido intermediate is identified in nitrene-transfer reactions by desorption electrospray ionization mass spectrometry (DESI-MS). DFT calculations show that low-lying FeIIIFeIII-.N-tosyl configurations play a major role in the high reactivity of the intermediate. Copyright

Enantioselective imidation of sulfides via enzyme-catalyzed intermolecular nitrogen-atom transfer

Engineering enzymes with novel reaction modes promises to expand the applications of biocatalysis in chemical synthesis and will enhance our understanding of how enzymes acquire new functions. The insertion of nitrogen-containing functional groups into unactivated C-H bonds is not catalyzed by known enzymes but was recently demonstrated using engineered variants of cytochrome P450BM3 (CYP102A1) from Bacillus megaterium. Here, we extend this novel P450-catalyzed reaction to include intermolecular insertion of nitrogen into thioethers to form sulfimides. An examination of the reactivity of different P450BM3 variants toward a range of substrates demonstrates that electronic properties of the substrates are important in this novel enzyme-catalyzed reaction. Moreover, amino acid substitutions have a large effect on the rate and stereoselectivity of sulfimidation, demonstrating that the protein plays a key role in determining reactivity and selectivity. These results provide a stepping stone for engineering more complex nitrogen-atom-transfer reactions in P450 enzymes and developing a more comprehensive biocatalytic repertoire.

Enantioselective nitrene transfer to sulfides catalyzed by a chiral iron complex

Iron works: Enantioselective nitrene transfer to sulfide was accomplished by a chiral iron(III)/PyBOX catalyst (see scheme). Various sulfimides were thus obtained in high enantioselectivities and yields. Applications of this protocol to the syntheses of enantioenriched sulfoximines and an epoxide were also demonstrated. Copyright