5349-15-5

Upstream product

• 133745-75-2 N-fluorobis(benzenesulfon)imide 
• 459-73-4 GlyOEt*HCl 
• 108-98-5 thiophenol 
• 970-88-7 2,4-dinitrophenyl benzenesulfonate 
• 98-09-9 benzenesulfonyl chloride 
• 623-33-6 glycine ethyl ester hydrochloride 

Downstream Products

• 133344-09-9 (1S,3S,4R)-2-Benzenesulfonyl-2-aza-bicyclo[2.2.1]hept-5-ene-3-carboxylic acid ethyl ester 
• 628724-21-0 4-(phenylsulfonyl)morpholine-2,6-dione 
• 17811-62-0 2,2'-((phenylsulfonyl)azanediyl)diacetic acid 

Relevant academic research and scientific papers

Synthesis of new organothiophosphorus insectoacaricides containing N-acylated amino acid fragments

Methods for the synthesis of O-alkyl S-(N-acyl-N-alkoxycarbonylalkyl)aminomethyl (methyl)thio- and -dithiophosphonates based on the reaction between alkaline-metal salts of O-alkyl (methyl)thio- and -dithiophosphonoates and N-alkoxycarbonyl-N-chloromethyl

Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols

Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.

Sulfonamide Synthesis through Electrochemical Oxidative Coupling of Amines and Thiols

Sulfonamides are key motifs in pharmaceuticals and agrochemicals, spurring the continuous development of novel and efficient synthetic methods to access these functional groups. Herein, we report an environmentally benign electrochemical method which enables the oxidative coupling between thiols and amines, two readily available and inexpensive commodity chemicals. The transformation is completely driven by electricity, does not require any sacrificial reagent or additional catalysts and can be carried out in only 5 min. Hydrogen is formed as a benign byproduct at the counter electrode. Owing to the mild reaction conditions, the reaction displays a broad substrate scope and functional group compatibility.

Regioselectivity and the nature of the reaction mechanism in nucleophilic substitution reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with primary amines

Second-order rate constants have been measured for the reaction of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of primary amines. The nucleophilic substitution reaction proceeds through competitive S-O and C-O bond fission pathways. The S-O bond fission occurs dominantly for reactions with highly basic amines or with substrates having a strong electron-withdrawing group in the sulfonyl moiety. On the other hand, the C-O bond fission occurs considerably for the reactions with low basic amines or with substrates having a strong electron-donating group in the sulfonyl moiety, emphasizing that the regioselectivity is governed by both the amine basicity and the electronic effect of the sulfonyl substituent X. The apparent second-order rate constants for the S-O bond fission have resulted in a nonlinear Bronsted-type plot for the reaction of 2,4-dinitrophenyl benzenesulfonate with 10 different primary amines, suggesting that a change in the rate-determining step occurs upon changing the amine basicity. The microscopic rate constants (k1 and k2/k-1 ratio) associated with the S-O bond fission pathway support the proposed mechanism. The second-order rate constants for the S-O bond fission result in good linear Yukawa-Tsuno plots for the aminolyses of 2,4-dinitrophenyl X-substituted benzenesulfonates. However, the second-order rate constants for the C-O bond fission show no correlation with the electronic nature of the sulfonyl substituent X, indicating that the C-O bond fission proceeds through an SNAR mechanism in which the leaving group departure occurs rapidly after the rate-determining step.

Nucleophilic reactivity towards electrophilic fluorinating agents: Reaction with N-fluorobenzenesulfonimide ((PhSO2)2NF)

Second-order rate constants for the reaction of N-fluorobenzenesulfonimide (FBS) with nucleophilic reagents, kNu (M-1 s-1), have been measured in aqueous solution at 25°C. Analysis of the reaction products shows that soft polarizable nucleophiles (I-, SCN-, Br-) react at fluorine, whereas hard nucleophiles (oxygen and nitrogen nucleophiles) react at sulfur. The ambident behaviour of this electrophile seems to be related to the relative contribution of electrostatic and orbital interactions in reaching the transition state. The preferential reaction of soft nucleophiles at fluorine and the correlation of kNu values with the one-electron oxidation potentials of the nucleophiles in water suggest that nucleophilic reactivity at fluorine is largely determined by the ease of one-electron transfer from the nucleophile to the electrophile. Nucleophilic addition to fluorine is far more sensitive to the nature of the attacking nucleophile than the corresponding reactions at both saturated (n scale) and unsaturated carbon (N+ scale). Comparison of the rate constants for the reaction of nucleophiles at the sulfonyl group with those for reaction of the same nucleophiles with 2,4-dinitrophenyl acetate reveals a similar reactivity pattern for sulfonyl sulfur and carbonyl carbon as electrophilic centres.

Diastereoselectivity and assignment of absolute stereochemistry in the aza-Diels-Alder reaction of a sulfonylimino acetate with 1-methoxy-3-trimethylsilyloxybuta-1,3-diene

N-imine 1b generated in situ from the corresponding brominated glycinate 4b reacts with Davishefsky's diene under thermal conditions to give a high yield of diastereoisomeric Diels-Alder adducts 7b and 6b in a 2.04:1 ratio.

IMINO DIELS-ALDER CYCLOADDITIONS: AN APPLICATION TO THE SYNTHESIS OF (+/-)-ARISTEROMYCIN

A formal synthesis of (+/-)-aristeromycin starting from the imino Diels-Alder cycloadduct 3a has been achieved with high overall yield.A novel method for the in situ preparation of N-sulfonylimines is reported.

Substitution Reactions of Alkanesulfonyl Derivatives: Direct Substitution vs. Elimination-Addition Mechanisms in Substitution Reactions of Alkyl α-Disulfones

The reactions of a series of alkyl and aralkyl α-sulfones, RSO2SO2R ( R = Me, n-Bu, i-Pr, ArCH2) with a variety of nucleophiles in aqueous dioxane have been examined.Both rates of reaction and whether a given reaction takes place by an elimination-addition (sulfene intermediate) or a direct substitution (attack of nucleophile on SO2 group of α-sulphone) mechanism have been determined.The great majority of substitution reactions of alkyl α-disulfones take place via an elimination-addition mechanism (eq 3a), with formation of a sulphene from the α-disulphone being rate determining.Only when nucleophile is one, like azide ion, that is weakly basic while still being a good nucleophile is a direct substitution the preferred pathway.Even with azide the reaction pathway changes to elimination-addition when the acidity of the hydrogens on the carbon adjacent to the sulfonyl group is increased sufficiently, as in (PhCH2SO2)2.Comparison of rates of elimination of α-disulphones (R'CH2SO2)2 with rates of base-catalyzed hydrogen exchange of the corresponding trifluoromethyl sulfones R'CH2SO2CF3 indicates that formation of sulfenes from α-disulfones involves either an irreversible E1cB or a very E1cB-like E2 mechanism, a conclusion that is also supported by the observed variation of the rate of elimination of RR'CHSO2SO2R'' with changes in R and R'.Comparison of the behavior of an alkyl α-disulfone with that of the corresponding alkanesulfonyl chloride reveals that changing Y in RCH2SO2Y from RSO2 to Cl causes direct substitution to be able to compete much more effectively with elimination-addition.Kinetic studies show that this arises because, for a given nucleophile, (a) elimination-addition is 5-10 times slower for the alkanesulfonyl chloride than for the α-disulfone while (b) the rate of direct substitution is 5-10 times faster for the sulfonyl chloride.The origin of these rate differences is discussed and explained.