13146-13-9

Upstream product

• 10439-23-3 4-methylbenzenesulfinyl chloride 
• 100-51-6 benzyl alcohol 
• 536-57-2 p-toluene sulfinic acid 
• 67-56-1 methanol 
• 18440-49-8 N-benzyl-N-p-toluenesulfonylhydrazine 
• 6996-92-5 benzeneseleninic acid 
• 880104-81-4 4-methyl-benzenesulfinic acid 2-iodo-benzyl ester 
• 38622-91-2 [(p-methylphenyl)sulfonylmethyl]isonitrile 
• 106-45-6 para-thiocresol 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 108549-23-1 Dibenzyl N,N-diisopropylphosphoramidite 
• 2943-42-2 di(4-methyl)phenylthiosulfonate 
• 1576-35-8 toluene-4-sulfonic acid hydrazide 
• 1666-17-7 benzaldehyde p-toluenesulfonylhydrazone 

Downstream Products

• 32884-74-5 3-[(4-methylphenyl)sulfanyl]-1H-indole 

Relevant academic research and scientific papers

Oxidation of 1,1-disubstituted hydrazines with benzeneseleninic acid and selenium dioxide. Facile preparation of tetrazenes

Various 1,1-disubstituted hydrazines were oxidized with benzeneseleninic acid in methanol, generally producing the corresponding tetrazenes in high yield.Studies of the by-products of the reaction, of the effects of protic vs. aprotic solvents, and trapping experiments suggest that N-aminonitrenes are unlikely intermediates in this oxidation.An alternative mechanism involving a Pummerer-like reaction of seleninamides derived from the hydrazines is proposed.Tetrazene formation fails when the hydrazine precursor contains an aryl or p-toluenesulfonyl substiuent, or when it is highly hindered.Selenium dioxide may be employed as the oxidant instead of the seleninic acid, but is generally less efficacious in achieving high tetrazene yields.

Sulfonyl-Promoted Michaelis-Arbuzov-Type Reaction: An Approach to S/Se-P Bonds

By facilitating the chemical conversion of thiols to thiosulfonates, phosphoramidite/phosphite bearing sp3-hybridized carbon serves as an ideal coupling material to forge new connections at room temperature. In this work, a functional group-induced, additive-free, novel, S-P bond-forming approach is presented. This protocol exhibits good functional group tolerance with wide applications that include phosphorylation of cysteine derivatives, development of a one-pot approach to mixed unsymmetrical thiophosphonates, and extension of the concept to different Se-P bonds. Meticulously, our reaction also generated a S-P bond against cyclic 1,2-dithiane-1-dioxide in a byproduct-free manner. These Michaelis-Arbuzov-type reactions are easy to conduct, work efficiently in a reduced reaction time, and are applicable to gram-scale preparation as well.

Efficient electrosynthesis of sulfinic esters via oxidative cross-coupling between alcohols and thiophenols

A new protocol for S O bond formation was developed by electrochemical oxidative cross-coupling between alcohols and thiophenols. With this strategy, a series of valuable sulfinic ester derivatives were synthesized up to 96% yield from basic starting materials. A preliminary mechanistic investigation reveals that this reaction involves oxygen reduction reaction (ORR).

Electrochemical synthesis of sulfinic esters from alcohols and thiophenols

Electrochemical oxidative couplings between S[sbnd]H and O[sbnd]H bonds are achieved herein directly from readily-available alcohols and thiophenols, affording a series of diverse sulfinic esters. This strategy can take advantage of 6 equivalents of alcohol, relative to thiophenol, to achieve moderate to good yields, without the assistance of any metallic catalysts, bases, and additional oxidants.

Base-Promoted Direct Synthesis of Sulfinates from N -Sulfonyl-hydrazones under Metal-Free Conditions

A base-promoted direct synthesis of sulfinates from N -sulfonylhydrazones is described. Various N -sulfonylhydrazones, derived from aldehydes and ketones, are converted into the corresponding sulfinates in moderate to good yields. This protocol possesses

Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited: Improved Synthesis and Revised Reaction Mechanism

Reaction of alcohols with sodium arenesulfinates could afford either sulfones or sulfinates, and O-attack of sulfinate anions onto the in situ generated carbocation intermediates from alcohols was the previous proposed reaction mechanism in many syntheses of sulfinates. This concept, which is often used consciously or unconsciously, was revised herein by using isotopic labeling experiments and development of an improved sulfinate synthesis. The improved sulfinate synthetic protocol possesses many advantages such as a high sulfinate/sulfone selectivity, a broad substrate scope, metal-free, and mild reaction conditions. The revised reaction mechanism necessitates revision of many previous proposed reaction mechanisms in literatures.

Wittig Ylide Mediated Decomposition of N -Sulfonylhydrazones to Sulfinates

N-Sulfonylhydrazones generate sulfinates selectively when treated with a stabilized Wittig ylide in a polar aprotic solvent at elevated temperature. The transition metal and base free decomposition method is applicable to N-sulfonylhydrazones generated from a number of aromatic and heteroaromatic aldehydes and ketones. In the case of N-tosylhydrazones derived from O-allyl and O-propargyl salicylaldehydes, selective formation of sulfinate occurs over intramolecular [3 + 2]-cycloaddition reaction.

Non-expensive, open-flask and selective catalytic systems for the synthesis of sulfinate esters and thiosulfonates

Two simple and efficient methods for the synthesis of sulfinate esters and thiosulfonates from sodium salts of sulfinic acids are described. Different alcohols were converted into the corresponding sulfinate esters in good yields and purity in an open flask. By the adjustment of the reaction conditions thiosulfonates could also be obtained in a very short reaction time.

Substrate- and temperature-controlled divergence in reactions of alcohols with TosMIC catalyzed by BF3 · Et2O: Facile access to sulfinates and sulfones

An efficient BF3 · Et2O-catalyzed divergent synthesis of sulfinate esters and sulfones through C–O and C–S bond formation has been achieved from alcohols and p-toluenesulfonylmethyl isocyanide (TosMIC). Various alcohols reacted smoothly with TosMIC under the present conditions at room temperature providing sulfinate esters exclusively. By tuning the reaction temperature, the alcohols that provide highly stabilized carbocation in the reaction medium afforded sulfones as sole products. This study was aimed at understanding the regioselectivity of ambidentate sulfinate ion and to elucidate the interpretation of sulfinate/sulfone scaffolds.

Sulfination of Alcohols with p-Toluenesulfonylmethyl Isocyanide under Metal-Free Conditions: A Mitsunobu Approach

A Mitsunobu approach for the synthesis of sulfinate esters by direct nucleophilic substitution of alcohols is described. The salient features of this strategy include neutral and metal-free conditions for the rapid synthesis of sulfinates in high yields. The present protocol using p-toluenesulfonylmethyl isocyanide (TosMIC) and the triphenylphosphine (TPP)/diisopropyl azodicarboxylate (DIAD) reagent system represents the general synthetic route to this important class of compounds. (Figure presented.).