- Selective Ortho Thiolation Enabled by Tuning the Ancillary Ligand in Palladium/Norbornene Catalysis
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Site-selective introduction of a sulfur group into aromatic compounds is essential and useful in organic, material, and pharmaceutical chemistry. A palladium/norbornene-catalyzed chemoselective ortho thiolation of aryl halides was reported. The selectivit
- Cai, Wenqiang,Gu, Zhenhua
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- Atom transfer radical addition to styrenes with thiosulfonates enabled by synergetic copper/photoredox catalysis
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A synergetic copper/photoredox catalyzed ATRA of styrenes and thiosulfonates is developed. Besides aryl ethylenes, the challenging α-substituted styrenes were employed to construct the benzylic quaternary carbon centers. Owing to the mild conditions as well as the high level of substrate compability, this ATRA could be applied to derivatize bioactive natural products in late stage, and to install fluorophores across alkenes. The mechanistic studies reveal sulfonyl radicals as the key intermediate in the transformation.
- Zhou, Xin,Peng, Zhiyuan,Wang, Peng George,Liu, Qingchao,Jia, Tiezheng
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supporting information
p. 1054 - 1059
(2021/02/01)
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- Thiosulfonylation of Unactivated Alkenes with Visible-Light Organic Photocatalysis
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A metal-free method for the vicinal thiosulfonylation of unactivated alkenes with thiosulfonates using 9-mesityl-10-methylacridinium perchlorate as the photo-organocatalyst with visible-light irradiation has been developed. The method can be performed in dimethyl carbonate under air at room temperature and features a broad functional group compatibility. Metrics indicate the green potential of the developed versus the state-of-the-art methodologies. Mechanistic studies revealed no single electron transfer but involvement of an energy transfer from the excited photo-organocatalyst to thiosulfonate reactant, subsequently providing a sulfenyl and a sulfonyl radical via homolytic cleavage.
- Abbaspour Tehrani, Kourosch,Ching, H. Y. Vincent,Gadde, Karthik,Guidetti, Andrea,Herrebout, Wouter A.,Maes, Bert U. W.,Mampuys, Pieter,Van Doorslaer, Sabine
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p. 8765 - 8779
(2020/09/21)
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- TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols: Construction of thiosulfonate under transition-metal free conditions
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A TFA promoted multi-component reaction of aryldiazonium with sodium metabisulphite and thiols to construct thiosulfonates under transition-metal free conditions is reported. The thiosulfonates were isolated in good yields with broad tolerance of function
- Huang, Cheng-Mi,Li, Jian,Wang, Shun-Yi,Ji, Shun-Jun
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supporting information
p. 1923 - 1926
(2020/01/13)
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- Electrochemical Oxidative Cross-Coupling Reaction to Access Unsymmetrical Thiosulfonates and Selenosulfonates
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The electrochemical oxidative cross-dehydrogenative coupling of arylsulfinic acids with thiophenols was achieved via a radical process. A wide range of arylsulfinic acids and substituted thiophenols were found to be tolerated, providing unsymmetrical thio
- Zhang, Xiaofeng,Cui, Ting,Zhang, Yanghao,Gu, Weijin,Liu, Ping,Sun, Peipei
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p. 2014 - 2019
(2019/03/26)
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- Unsymmetrical Organotrisulfide Formation via Low-Temperature Disulfanyl Anion Transfer to an Organothiosulfonate
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New methodology is presented for the formation of unsymmetrical organotrisulfides in a high yield and purity, relatively free of polysulfide byproducts. The highlight of the method is the low-temperature (-78 °C) deprotection of a disulfanyl acetate with sodium methoxide in THF to form a disulfanyl anion, which reacts rapidly in situ with an organothiosulfonate (S-aryl or S-alkyl) within 30 seconds followed by quenching. The discovery of these new reaction conditions together with the relative greenness of the chemistry overall makes for an efficient protocol, from which a range of organotrisulfides covering aliphatic, aromatic, as well as cysteine and sugar groups can be accessed in a high yield and purity.
- Ali, Doaa,Hunter, Roger,De Doncker, Stephen,Rees-Jones, Sophie C. M.,Kaschula, Catherine H.
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p. 2862 - 2869
(2019/03/23)
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- PTAB mediated open air synthesis of sulfonamides, thiosulfonates and symmetrical disulfanes
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A facile methodology has been described which has successfully simplified the generation of sulfonamides, thiosulfonates and symmetric disulfanes. This “trio” of reactions occur in an open air metal free atmosphere and has also been scaled up to grams making it suitable for commercialization. The reactions also have been successfully carried out with asymmetric variants, thus contributing to the chiral pool. The user friendly “trio” enables easy generation of these versatile sulfur analogues and the reaction condition employed depict an economic outline.
- Sarkar, Debayan,Ghosh, Manoj Kumar,Rout, Nilendri
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p. 2360 - 2364
(2018/05/24)
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- H2O2-mediated metal-free protocol towards unsymmetrical thiosulfonates from sulfonyl hydrazides and disulfides in PEG-400
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A green and practical protocol between sulfonyl hydrazides and disulfides is herein reported for the synthesis of unsymmetrical thiosulfonates with the assistance of H2O2 in PEG-400, releasing N2 and H2O as the byproducts. The efficient and compatible process was considered to take place in the absence of metallic catalysts through a radical mechanism as determined by EPR analysis.
- Peng, Zhihong,Zheng, Xiao,Zhang, Yingjun,An, Delie,Dong, Wanrong
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supporting information
p. 1760 - 1764
(2018/04/30)
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- Copper-Catalyzed TBHP-Mediated Radical Cross-Coupling Reaction of Sulfonylhydrazides with Thiols Leading to Thiosulfonates
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A tert-butyl hydroperoxide (TBHP)-mediated coupling of sulfonylhydrazides with thiols catalyzed by CuBr2 to afford thiosulfonates via a radical process is described.
- Zhang, Guo-Yu,Lv, Shuai-Shuai,Shoberu, Adedamola,Zou, Jian-Ping
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p. 9801 - 9807
(2017/09/22)
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- Iron(III)-Catalyzed Radical Cross-Coupling of Thiols with Sodium Sulfinates: A Facile Access to Thiosulfonates
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A convenient and efficient synthesis of symmetrical and asymmetric thiosulfonates from thiols and sodium sulfinates is reported. The protocol involves iron(III)-catalyzed formation of sulfenyl and sulfonyl radicals in situ under aerobic conditions and their subsequent cross-coupling to afford thiosulfonates in 83-96% yield. The utilization of readily available, nontoxic, and inexpensive iron(III) as a catalyst and atmospheric oxygen as an oxidant is within the confines of green and sustainable chemistry.
- Keshari, Twinkle,Kapoorr, Ritu,Yadav, Lal Dhar S.
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p. 1878 - 1882
(2016/07/16)
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- NBS-promoted sulfenylation of sulfinates with disulfides leading to unsymmetrical or symmetrical thiosulfonates
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A highly practical method to access unsymmetrical and symmetrical thiosulfonates in moderate to excellent yields has been developed through NBS-promoted sulfenylation of sulfinates with disulfides. The present process enables the use of two RS in RSSR and shows broad functional group tolerance, which represents an atom-economical and practical procedure for the synthesis of thiosulfonates. A plausible mechanism for the role of NBS as a promoter for the cleavage of disulfides generating N-(organothio)succinimide that then undergos facile sulenylation with sulfinates is proposed. Copyright
- Liang, Gaigai,Liu, Miaochang,Chen, Jiuxi,Ding, Jinchang,Gao, Wenxia,Wu, Huayue
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experimental part
p. 1611 - 1616
(2012/09/07)
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- New and facile synthesis of thiosulfonates from sulfinate/disulfide/I2 system
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Thiosulfonates were prepared by the iodine oxidative sulfenylation of sulfinates with various disulfides in good yields both in the presence and absence of solvent. One of the important biological applications of sulfenylation is the reaction of cyclic disulfides.
- Fujiki, Kiyoko,Tanifuji, Naoki,Sasaki, Yohei,Yokoyama, Taku
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p. 343 - 348
(2007/10/03)
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