Metal-free C–H thioarylation of arenes using sulfoxides: a direct, general diaryl sulfide synthesis

Fernández‐Salas, José A.; Pulis, Alexander P.; Procter, David J.

doi:10.1039/c6cc07627k

Cited by 91 publications

(47 citation statements)

References 92 publications

(10 reference statements)

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“…Most likely, in the case of methyl phenyl sulfoxide ( 2 b ) the conversion stops on the stage of a polar sulfoxonium intermediate, which is demethylated by means of DBU to furnish 4 b . This result was consistent with the literature reported by Procter . The yield of 3‐chlorinated indole 3 a was increased up to 64% by using TMSCl and ethyl phenyl sulfoxide ( 2 c ), meanwhile, ethyl phenyl sulfide ( 4 a ) was also obtained in 60% yield (entry 3).…”

Section: Methodssupporting

confidence: 91%

“…Based on the related reports in the literature, a plausible reaction mechanism for the chlorination of indoles 1 with TMSCl and sulfoxide 2 c is illustrated in Scheme . Sulfoxide 2 c was activated by TMSCl to form sulfoxonium salt 7 .…”

Section: Methodsmentioning

confidence: 99%

“…This result was consistent with the literature reported by Procter. [14] The yield of 3-chlorinated indole 3 a was increased up to 64% by using TMSCl and ethyl phenyl sulfoxide (2 c), meanwhile, ethyl phenyl sulfide (4 a) was also obtained in 60% yield (entry 3). The yield of 3chlorinated indole 3 a was further increased up to 76% when the loading of TMSCl was increased from 1.0 to 2.0 equivalents (entries [3][4][5].…”

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confidence: 99%

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Sulfoxide‐Promoted Chlorination of Indoles and Electron‐Rich Arenes with Chlorine as Nucleophile

Wang²,

Zhang

et al. 2020

Adv Synth Catal

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An efficient chlorination of indoles and electron‐rich arenes with chlorine anion as nucleophile is described. With the use of ethyl phenyl sulfoxide as the promoter, the reaction went smoothly under metal‐free and mild conditions. Various indoles and electron‐rich arenes are converted into the corresponding chlorinated compounds in moderate to excellent yields. A plausible interrupted Pummerer reaction mechanism was proposed without the oxidation of chloride anion. In addition, the byproduct thioether could be easily converted to the starting material sulfoxide just by a simple oxidation reaction.

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Section: Methodssupporting

confidence: 91%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Sulfoxide‐Promoted Chlorination of Indoles and Electron‐Rich Arenes with Chlorine as Nucleophile

Wang²,

Zhang

et al. 2020

Adv Synth Catal

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“…Recently, we34353637383940 and others41424344454647484950515253545556 reported the metal-free, sulfoxide directed57 C–H functionalization of a variety of molecular scaffolds, which was enabled by an interrupted Pummerer reaction28. Spurred on by these recent achievements, we considered the use of benzothiophene S -oxides 1 for the synthesis of important C3-functionalized benzothiophenes, as the corresponding sulfonium salts I and II , formed after reaction with the coupling partners, lack aromaticity about the five-membered ring and should therefore undergo facile C–C bond formation via [3,3]-sigmatropic rearrangement58, thus delivering unexplored reactivity not accessible in benzothiophenes.…”

Section: Resultsmentioning

confidence: 99%

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

et al. 2017

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Benzothiophenes are heterocyclic constituents of important molecules relevant to society, including those with the potential to meet modern medical challenges. The construction of molecules would be vastly more efficient if carbon–hydrogen bonds, found in all organic molecules, can be directly converted into carbon–carbon bonds. In the case of elaborating benzothiophenes, functionalization of carbon–hydrogen bonds at carbon-number 3 (C3) is markedly more demanding than at C2 due to issues of regioselectivity (C3 versus C2), and the requirement of high temperatures, precious metals and the installation of superfluous directing groups. Herein, we demonstrate that synthetically unexplored but readily accessible benzothiophene S-oxides serve as novel precursors for C3-functionalized benzothiophenes. Employing an interrupted Pummerer reaction to capture and then deliver phenol and silane coupling partners, we have discovered a directing group-free method that delivers C3-arylated and -alkylated benzothiophenes with complete regioselectivity, under metal-free and mild conditions.

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“…Aryldimethylsulfonium salts can be also prepared from simple arenes through Procter's method . Treatment of Triphenylamine with DMSO and Tf 2 O afforded the corresponding arylsulfonium salt 29 (Scheme ).…”

Section: Reductive Carboxylation Of C−s Bond With Co2mentioning

confidence: 99%

Catalytic Carbonylation and Carboxylation of Organosulfur Compounds via C−S Cleavage

Nogi

Yorimitsu

2020

Chemistry An Asian Journal

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Transition‐metal‐catalyzed carbonylation with CO gas occupies a privileged position in organic synthesis for the synthesis of carbonyl compounds. Although this attractive and useful chemistry has led many researchers to investigate carbonylative transformations of various organic (pseudo)halides, C−S‐cleaving carbonylation of organosulfur compounds has been fairly limited. Recently, a broad spectrum of C−S‐cleaving transformations has been emerging in the field of cross‐coupling. In light of the importance of carbonyl compounds as well as considerable advancement for employing organosulfur compounds as competent surrogates of (pseudo)halides, carbonylative transformations of C−S bonds should be of high value. This Minireview focuses on catalytic C−S carbonylation of organosulfur compounds with CO or its equivalents. In addition, reductive carboxylation of C−S bonds with CO2 is described.

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Metal-free C–H thioarylation of arenes using sulfoxides: a direct, general diaryl sulfide synthesis

Cited by 91 publications

References 92 publications

Sulfoxide‐Promoted Chlorination of Indoles and Electron‐Rich Arenes with Chlorine as Nucleophile

Sulfoxide‐Promoted Chlorination of Indoles and Electron‐Rich Arenes with Chlorine as Nucleophile

Regioselective synthesis of C3 alkylated and arylated benzothiophenes

Catalytic Carbonylation and Carboxylation of Organosulfur Compounds via C−S Cleavage

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