- DABCO-promoted Diaryl Thioether Formation by Metal-catalyzed Coupling of Sodium Sulfinates and Aryl Iodides
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A scalable catalytic synthesis method using commodity chemicals for constructing diaryl thioethers directly from sodium arylsulfinates and iodoarenes is reported in this study. In the presence of CuO or other copper salts such as Cu(OAc)2 as well as palladium catalysts, DABCO demonstrated to be essential to promote this transformation. Various iodoarenes and aryl sulfinates were examined and demonstrated the viability of this method. The mechanistic study showed that radical reactions occurred, while DABCO N-oxide radical can be observed by mass spectrometry. A plausible catalytic mechanism involving DABCO is also discussed, suggesting synergistic reduction of sulfinate by Cu(II) and DABCO is the key step of this coupling reaction. (Figure presented.).
- Liu, Yanpeng,Lam, Long Yin,Ye, Jiqing,Blanchard, Nicolas,Ma, Cong
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supporting information
p. 2326 - 2331
(2020/05/05)
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- Ring-Closing Synthesis of Dibenzothiophene Sulfonium Salts and Their Use as Leaving Groups for Aromatic 18F-Fluorination
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Herein, we report a novel intramolecular ring-closing reaction of biaryl thioethers that give access to highly functionalized dibenzothiophene sulfonium salts under mild conditions. The resulting precursors react regioselectively with [18F]fluo
- Gendron, Thibault,Sander, Kerstin,Cybulska, Klaudia,Benhamou, Laure,Sin, Pak Kwan Brian,Khan, Aqsa,Wood, Michael,Porter, Michael J.,?rstad, Erik
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p. 11125 - 11132
(2018/09/11)
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- Triphenylsulfonium topophotochemistry
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The products from the 193 nm irradiation of triphenylsulfonium nonaflate (TPS) embedded in a poly(methyl methacrylate) (PMMA) film have been characterized. The analysis of the photoproduct formation was performed using chromatographic techniques including HPLC, GPC and GC-MS as well as UV-vis and NMR spectroscopic methods. Two previously unreported TPS photoproducts, triphenylene and dibenzothiophene, were detected; additionally, GPC and DOSY-NMR spectroscopic analyses after irradiation suggested that TPS fragments had been incorporated into the polymer film. The irradiation of acetonitrile solutions containing 10% w/v PMMA and 1% w/v TPS in a 1 cm-path-length cuvette showed only a trace amount of triphenylene or dibenzothiophene, indicating that topochemical factors were important for the formation of these molecules. The accumulated evidence indicates that both products were formed by in-cage, secondary photochemical reactions: 2-(phenylthio)biphenyl to triphenylene, and diphenylsulfide to dibenzothiophene.
- Despagnet-Ayoub,Kramer,Sattler,Sattler,Labeaume,Thackeray,Cameron,Cardolaccia,Rachford,Winkler,Gray
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- One-pot synthesis of symmetrical and unsymmetrical aryl sulfides by Pd-catalyzed couplings of aryl halides and thioacetates
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Aryl sulfides were obtained from the coupling reaction of S-aryl (or S-alkyl) thioacetates and aryl bromides in the presence of palladium catalyst. This reaction method enables the one-pot synthesis of symmetrical and unsymmetrical diaryl sulfides by employing potassium thioacetate with aryl iodides and aryl bromides.
- Park, Namjin,Park, Kyungho,Jang, Mihee,Lee, Sunwoo
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experimental part
p. 4371 - 4378
(2011/07/06)
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- A novel electron beam-induced reaction of sulfonium salt in the crystalline state
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The electron beam irradiation of triphenylsulfonium methanesulfonate in the crystalline state provides a new benzene-substituted sulfonium salt. This product has not been observed either by photolysis in the crystalline state nor by electron beam irradiation in a solution. The formation of the substitution product was confirmed by GC-MS analysis.
- Moon, Seongyun,Maekawa, Yasunari,Yoshida, Masaru
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p. 408 - 409
(2007/10/03)
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- Reactions of Selenurane with Alcohols, Thiols and Selenol. A Quest for Formation of a New ?-Selenurane , or
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Bis(2,2'-biphenylylene)selenurane readily reacts with various alcohols, phenols, thiols and selenol to give ligand coupling or ipso-substitution products under mild conditions via a two-step mechanism involving a ?-selenurane , and or corresponding selenonium salts as intermediates.
- Sato, Soichi,Furukawa, Naomichi
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p. 889 - 892
(2007/10/02)
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- Photochemical reaction of onium salts with N,N-dimethylaniline: Evidence for photoinduced electron transfer
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Direct photolysis of diphenyliodonium salts gives significantly more iodobiphenyls than in the presence of dimethylaniline. An electron transfer reaction from the singlet excited state of dimethylaniline is proposed.
- Buijsen,Hacker
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p. 1557 - 1560
(2007/10/02)
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- Photochemistry of triarylsulfonium salts
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The photolysis of triphenylsulfonium, tris(4-methylphenyl)sulfonium, tris(4-chlorophenyl)sulfonium, several monosubstituted (4-F, 4-Cl, 4-Me, 4-MeO, 4-PhS, and 4-PhCO), and disubstituted (4,4′-Me2 and 4,4′-(MeO)2) triphenylsulfonium salts was examined in solution. It was found that direct irradiation of triphenylsulfonium salts produced new rearrangement products, phenylthiobiphenyls, along with diphenyl sulfide, which had been previously reported. Similarly, the triarylsulfonium salts, with the exception of the [4-(phenylthio)phenyl]diphenylsulfonium salts, gave the new rearrangement products. The mechanism for direct photolysis is proposed to occur from the singlet excited state to give a predominant heterolytic cleavage along with some homolytic cleavage. The heterolytic cleavage gives phenyl cation and diphenyl sulfide, whereas homolytic cleavage gives the singlet phenyl radical and diphenylsulfinyl radical cation pair. These pairs of intermediates then produce the observed photoproducts by an in-cage recombination mechanism and also by reactions with the solvent. The effect of solvent viscosity, solvent polarity, anion, and aryl substituent was examined. The triplet sensitization of the sulfonium salts was also investigated. In contrast to previous reports, the triplet state of the sulfonium salt is labile, leading to a triplet geminate radical pair of phenyl radical and diphenylsulfinyl radical cation. These species ultimately form benzene and diphenyl sulfide as products. Direct photolysis of the [4-(phenylthio)phenyl]diphenylsulfonium salt, gave exclusively diphenyl sulfide, benzene, and acid and decomposes via the triplet excited state.
- Dektar, John L.,Hacker, Nigel P.
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p. 6004 - 6015
(2007/10/02)
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- CATIONIC PHOTOINITIATORS: SOLID STATE PHOTOCHEMISTRY OF TRIPHENYLSULFONIUM SALTS
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Triphenylsulfonium bromide, triflate, tetrafluoroborate, hexafluoroarsenate, hexafluorophosphate and hexafluoroantimonate were irradiated in solution and in the solid state.The photoproducts, 2-, 3- and 4-phenylthiobiphenyl are formed by an in-cage fragmentation-recombination mechanism, whereas diphenylsulfide is formed by a cage-escape reaction.In dilute solution, the ratio of cage to escape products is approximately one for each salt.Also in concentrated solutions, an identical cage:escape ratio is observed for all salts except for the bromide, which favors the escape reaction.Photolysis of the salts in the solid state shows remarkable counter ion dependence and cage:escape ratios as high as 5:1 are observed.The mechanism for both in-cage and escape reactions is described.
- Hacker, Nigel P.,Leff, Daniel V.,Dektar, John L.
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p. 505 - 511
(2007/10/02)
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- Triphenylsulfonium Salt Photochemistry. New Evidence for Triplet Excited State Reactions
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Direct and sensitized photolysis of triphenylsulfonium salts can generate the triplet state which yields diphenyl sulfide as the major photoproduct.Triplet sensitization is observed in the presence of ketones with ET > 74 kcal/mol, and the efficiency of sensitization correlates qualitatively with increasing ET of the sensitizer.In contrast, the singlet excited state yields mainly (phenylthio)biphenyls in addition to diphenyl sulfide.
- Dektar, John L.,Hacker, Nigel P.
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p. 1833 - 1835
(2007/10/02)
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- A New Mechanism for Photodecomposition and Acid Formation from Triphenylsulphonium Salts
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A new photodecomposition pathway for triphenylsulphonium salts yields phenylthiobiphenyls by a cage fragmentation-recombination process as major products, in addition to diphenyl sulphide; a new mechanism for acid formation is described.
- Dektar, John L.,Hacker, Nigel P.
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p. 1591 - 1592
(2007/10/02)
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