A general and mild two-step procedure for the synthesis of aryl and heteroaryl sulfonamides from the corresponding iodides

Ho, Danny K. H.; Chan, Lily; Hooper, Alice; Brennan, P.E.

doi:10.1016/j.tetlet.2010.12.050

Cited by 33 publications

(21 citation statements)

References 8 publications

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“…[50][51][52][53][54][55][56][57][58] Their use in chemistry relies mainly on their facile chemical reduction, [50][51][52][53][54][55][56][57][58] which has been shown to lead to various products through a reaction with a wide range of reagents, and on the readiness to replace the Cl with various substituents. [50][51][52][53][54][55][56][57][58] Despite this wide use of sulfonyl chlorides under reductive conditions, the ET to these compounds and the factors controlling it are still not well understood. A number of electrochemical investigations have been reported in different media but a clear picture of the details of the reduction mechanism is still lacking.…”

Section: Introductionmentioning

confidence: 99%

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Houmam

Hamed

2012

Phys. Chem. Chem. Phys.

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Important aspects of the electrochemical reduction of a series of substituted arene sulfonyl chlorides are investigated. An interesting autocatalytic mechanism is encountered where the starting material is reduced both at the electrode and through homogeneous electron transfer from the resulting sulfinate anion. This is due to the homogenous electron transfer from the two-electron reduction produced anion (arene sulfinate) to the parent arene sulfonyl chloride. As a result, the reduction process and hence the generated final products depend on both the concentration of the substrate and the scan rate. A change is also observed in the reductive cleavage mechanism as a function of the substituent on the phenyl ring of the arene sulfonyl chloride. With 4-cyano and 4-nitrophenyl sulfonyl chlorides a "sticky" dissociative ET mechanism takes place where a concerted ET mechanism leads to the formation of a radical/anion cluster before decomposition. With other substituents (MeO, Me, H, Cl, and F) a "classical" dissociative ET is followed, where the ET and bond cleavage are simultaneous. The dissociative electron transfer theory, as well as its extension to the case of strong in-cage interactions between the produced fragments, along with gas phase chemical quantum calculations results helped us to rationalize both the observed change in the ET mechanism and the occurrence of the "sticky" dissociative ET mechanism. The radical/anion pair interactions have been determined both in solution as well as in the gas phase. The study also shows that despite the low magnitude of in-cage interactions in acetonitrile compared to the gas phase their existence strongly affects the dynamics of the involved reactions. It also shows that, as expected, these interactions are reinforced by the existence of strong electron-withdrawing substituents. The occurrence of an autocatalytic process and the existence of the radical/anion interaction may explain the differences previously observed in the reduction of these compounds in different media.

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Section: Introductionmentioning

confidence: 99%

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Houmam

Hamed

2012

Phys. Chem. Chem. Phys.

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“…Several one‐pot methods for the synthesis of sulfonamides proceeding through oxidative chlorination of thiols with subsequent nucleophilic substitution of the chlorine atom are described below. Thus, a one‐pot synthesis of sulfonamides 71 from S ‐aryl thiobenzoates 69 and amines 70 with trichloroisocyanuric acid (TCCA) as a chlorinating agent (Scheme ) was reported …”

Section: Synthesis Of Sulfonamidesmentioning

confidence: 99%

Oxidative Coupling with S–N Bond Formation

2018

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Oxidative strategies are a powerful tool in organic synthesis for the formation of heteroatom–heteroatom, carbon–heteroatom, and carbon–carbon bonds. Among these processes the reactions of oxidative S–N bond formation deserve considerable interest as convenient, effective, and environmentally friendly alternatives to existing methods for the synthesis of a great variety of organic compounds widely used in organic and medicinal chemistry. These transformations take place through the interaction of S‐ and N‐reagents and an oxidant, by radical or ionic mechanisms. Sulfinic acids and their salts, thiols, sulfonyl hydrazides, and thiosulfonates are generally used as S‐reagents; aliphatic and aromatic amines are usually applied as N‐reagents. The role of the oxidant mostly lies in the oxidation of the S‐reagent, after which the formed active species reacts with the N‐reagent to result in the S–N coupling product. There are two versions of oxidative S–N coupling processes: the intermolecular variant opens simple pathways to sulfen‐, sulfin‐, and sulfonamides, sulfenyl‐ and sulfoximines, sulfanes, and sulfur diimides, whereas the intramolecular one leads to the formation of various heterocycles. Of the major problems associated with successful performance of oxidative S–N coupling reactions, the first relates to the search for coupling partners that will work together to form a new bond under oxidative conditions. The second is the choice of a suitable oxidative system that will not overoxidize starting compounds. That is why mild oxidants, such as hypervalent iodine compounds and copper salts and complexes, are generally applied in these processes. This is the first exhaustive review relating to achievements in oxidative transformations involving S–N bond formation. It summarizes 134 references, mainly from 2000 to 2018, and is divided into chapters according to the classes of compounds synthesized.

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“…Sulfonyl chlorides are the most prevalent reagents for the installation of the sulfonyl protecting group [ 1 ], which can be converted into numerous sulfonyl derivatives [ 2 , 3 , 4 , 5 , 6 ], undergo diverse desulfitative cross-couplings [ 7 , 8 ], and serve as arylating agents [ 9 , 10 , 11 , 12 , 13 ]. In addition, they have been widely used as important building blocks for the manufacture of elastomers, pharmaceuticals, dyes, detergents, ion exchange resins, and herbicides [ 14 , 15 , 16 ].…”

Section: Introductionmentioning

confidence: 99%

Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

Chen

Shen

et al. 2021

Molecules

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A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.

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A general and mild two-step procedure for the synthesis of aryl and heteroaryl sulfonamides from the corresponding iodides

Cited by 33 publications

References 8 publications

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Application of the dissociative electron transfer theory and its extension to the case of in-cage interactions in the electrochemical reduction of arenesulfonyl chlorides

Oxidative Coupling with S–N Bond Formation

Facile Synthesis of Sulfonyl Chlorides/Bromides from Sulfonyl Hydrazides

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