57671-12-2

Upstream product

• 123-75-1 pyrrolidine 
• 1858-86-2 Ethyl p-toluenesulfinate 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 536-57-2 p-toluene sulfinic acid 
• 6873-55-8 p-tolylsulfinyl amide 
• 68388-05-6 O-benzoyl-N-hydroxylpyrrolidine 
• 672-78-6 methyl p-toluene sulfinate 
• 98-59-9 p-toluenesulfonyl chloride 
• 103-19-5 di(p-tolyl) disulfide 
• 106-45-6 para-thiocresol 

Downstream Products

• 123-75-1 pyrrolidine 
• 672-78-6 methyl p-toluene sulfinate 
• 6435-78-5 N-tosylpyrrolidine 
• 536-57-2 p-toluene sulfinic acid 
• 151647-54-0 3-phenyl-1-pyrrolidin-1-yl-propane-1-one 
• 64353-47-5 (+)-(S)-N-p-tolylsulfinylpyrrolidine 
• 5056-07-5 (S)-methyl p-tolyl sulfoxide 

Relevant academic research and scientific papers

Rare-Earth-Catalyzed Transsulfinamidation of Sulfinamides with Amines

A rare-earth-catalyzed transsulfinamidation of primary sulfinamides with alkyl, aryl, and heterocyclic amines for the synthesis of diverse secondary and tertiary sulfinamides has been realized. Unlike transition metal-catalyzed cross-coupling approaches restricted to non-commercially available disubstituted O-benzoyl hydroxylamines, this newly developed protocol is suitable for diverse readily available primary and secondary amines without any modifications. Excellent catalytic activity and selectivity are achieved with Eu(OTf)3 under mild reaction conditions, which extends the applicability of rare-earth catalysis.

Synthetic preparation of N-alkyl and N-aryl arenesulfinamides using an arenesulfinic acid-CDI driven approach

A new synthetic methodology has been developed for the synthesis of N-alkyl and N-aryl arenesulfinamides. The methodology involved reacting arenesulfinic acids (R = -Me, -H, -Cl) with 1,1’-carbonyldiimidazole (CDI) to form the reactive intermediate, an arenesulfinylimidazole. This intermediate was then reacted with both primary and secondary amines to yield the corresponding N-alkyl sulfinamides in yields up to 90%. While the overall yields ranged from 52% to 90%, the level of diastereoselection with racemic or enantiomerically enriched amines only reached a level of 54:46 favoring the major diastereomer as determined by analysis of the 500 MHz 1H NMR spectra. A series of aniline derivatives were also investigated as coupling partners and were found to form the N-aryl arenesulfinamide in good yield.

Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines for direct access to sulfinamides

It was reported to develop a simple and convenient method for the Ni/NHC-catalyzed cross-coupling of methyl sulfinates and amines without an acid/base to afford secondary or tertiary sulfinamides in moderate to good yields. The method can provide the desired products with broad substrate scope, good chemoselectivity and good functional group compatibility. The presented approach may enrich the Ni/NHC catalyst system and promote the applications of methyl sulfinates in the organic sulfur chemistry.

Efficient Synthesis of Sulfinate Esters and Sulfinamides via Activated Esters of p -Toluenesulfinic Acid

Sulfinate esters were prepared by the process of activating p -toluenesulfinic acid with either cyanuric chloride, methanesulfonyl chloride, or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC-HCl). Activation of p -toluenesulfinic acid with cyanuric chloride led to the formation of sulfinate esters that were accompanied by the formation of the corresponding sulfones. The use of methanesulfonyl chloride for activation via methanesulfonic p -toluenesulfinic anhydride afforded mixtures of sulfinate esters and methanesulfonates. The use of the carbodiimide EDC proved to yield the best results with the highly selective formation of the target sulfinate esters. The use of trimethylacetic p -toluenesulfinic anhydride or cyanuric chloride to achieve the synthesis of sulfinamides proved to be ineffective due to poor chemoselectivity of the nucleophilic attack on the activated p -toluenesulfinic acid anhydride. Ultimately, the use of EDC-HCl to form the sulfinamides proved to be the best pathway for synthesis.

Copper-Catalyzed Transsulfinamidation of Sulfinamides as a Key Step in the Preparation of Sulfonamides and Sulfonimidamides

Secondary or tertiary sulfinamides are prepared by copper-catalyzed transsulfinamidation of primary sulfinamides with O-benzoyl hydroxylamines. Subsequent oxidations of the resulting products lead to the corresponding sulfonamides. Treatment of N-aryl sulfinamides with O-benzoyl hydroxylamines under copper catalysis provides N-aryl sulfonimidamides.

Copper-Catalyzed Oxidative Synthesis of Sulfinamides Using Thiols or Disulfides with Amines

Copper-catalyzed coupling of thiols with amines was used to synthesize numerous sulfinamides in excellent yields. Sulfenamides or sulfonamides were also formed as reaction byproducts albeit in trace quantities. The procedure is carried out as a one step a

One-pot synthesis of sulfonamides from methyl sulfinates using ultrasound

Room temperature ultrasonic irradiation of neat mixtures of methyl sulfinates and primary or secondary amines (1.5 equiv) produced sulfinamides, which on m-CPBA oxidation (in dichloromethane) were converted into the corresponding sulfonamides. The two steps can be accomplished in one pot, in good overall yields, when using secondary amines, but primary amines give better sulfonamide yields when the peracid oxidation is effected on the purified sulfinamide. This constitutes a mild, efficient, and potentially scalable route to sulfonamides, which obviates the use of water sensitive, often lachrymatory sulfonyl chlorides and large reagent excesses.

Expedient synthesis of sulfinamides from sulfonyl chlorides

Sulfinamides were synthesized from sulfonyl chlorides using a procedure involving in situ reduction of sulfonyl chlorides. The reaction is broad in scope and easy to perform.

Electrochemical oxidation of N-p-toluenesulfinamides

Matrix presented Contrasting and interesting electrochemical behavior is observed in anodic oxidation of N-substituted p-toluenesulfinamides under controlled current conditions. For sulfinamides derived from secondary alkylamines and primary arylamines, the N-sulfinyl group is removed and the corresponding amines are formed; for sulfinamides derived from primary alkylamines, sulfur oxidation yields the corresponding sulfonamides in good yields.