- Visible-Light-Induced Radical Cascade Reaction of 1-Allyl-2-ethynylbenzoimidazoles with Thiosulfonates to Assemble Thiosulfonylated Pyrrolo[1,2-a]benzimidazoles
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A visible-light-induced radical domino reaction of 1-allyl-2-ethynylbenzoimidazoles with thiosulfonates was developed, which generated the thiosulfonylated pyrrolo[1,2-a]benzimidazoles in moderate to good yields. This reaction proceeded under transition-metal-free conditions with good functional group tolerance and high regioselectivity. The possible pathway involved thiosulfonates were activated through the energy transfer route promoted by photocatalysis.
- Liu, Yan,Zhang, Niuniu,Xu, Yanli,Chen, Yanyan
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p. 16882 - 16891
(2021/11/18)
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- An iodine-mediated new avenue to sulfonylation employingN-hydroxy aryl sulfonamide as a sulfonylating agent
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A novel and highly efficient I2/K2CO3mediated regioselective sulfonylation of thiophenols, aryl acetylenic acid and aromatic alkynes withN-hydroxy sulfonamide has been developed.N-hydroxy sulfonamide has been used for the first time for the synthesis of these sulfones. The scope and versatility of the reaction has been demonstrated by the regio- and stereoselective synthesis of different analogs of sulfones with various structural features.
- Raghuvanshi, Dushyant Singh,Verma, Narsingh
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supporting information
p. 4760 - 4767
(2021/06/09)
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- Preparation method of thiosulfonate compound
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The invention belongs to the field of organic synthetic chemistry, and particularly discloses a preparation method of a thiosulfonate compound. The specific preparation process comprises the following steps: taking aryl diazonium salt, sodium pyrosulfite and thiophenol/mercaptan as raw materials, taking organic dye as a photocatalyst, adding an organic solvent, and reacting for 12 hours at room temperature under the irradiation of an LED visible light lamp and nitrogen protection to generate thiosulfonate; and after the reaction is finished, adding distilled water into the reaction system, extracting the reaction liquid with ethyl acetate, concentrating the extraction liquid to obtain a crude product, and carrying out silica gel column chromatography separation on the crude product to obtain thiosulfonate. According to the method, simple and easily available sodium pyrosulfite is used as a sulfone source, cheap organic dye is used as a photocatalyst, clean light energy is used as a reaction energy source, a high-energy-consumption heating device and a metal catalyst or strong acid are not used, the reaction condition is mild, the operation is simple and convenient, and a green synthesis strategy is provided for thiosulfonate.
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Paragraph 0031-0080
(2021/05/19)
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- The organocatalytic synthesis of perfluorophenylsulfides: Via the thiolation of trimethyl(perfluorophenyl)silanes and thiosulfonates
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The organic superbase t-Bu-P4-catalyzed direct thiolation of trimethyl(perfluorophenyl)silanes and thiosulfonates was developed. Yields of perfluorophenylsulfides of up to 97% under catalysis of 5 mol% t-Bu-P4 were achieved. This method was shown to provide an efficient way to construct the perfluorophenyl-sulfur bond under mild metal-free reaction conditions. This journal is
- Cai, Zhihua,Du, Guangfen,He, Lin,Lin, Muze,Luo, Jinyun,Wu, Leifang
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supporting information
p. 9237 - 9241
(2021/11/13)
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- Visible-Light-Induced Cyclization/Aromatization of 2-Vinyloxy Arylalkynes: Synthesis of Thio-Substituted Dibenzofuran Derivatives
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A visible-light-induced cascade reaction of 2-vinyloxy arylalkynes with thiosulfonates was developed and provided unexpected thio-substituted dibenzofuran derivatives in moderate yields. Mechanistic studies revealed the thiosulfonylation product of 2-vinyloxy arylalkyne was the key intermediate, and the additive disulfide played the role of hydrogen abstraction in the aromatization process to offer the desired product. This reaction presents a new reaction mode for the construction of polycyclic oxygen heterocycles.
- Chen, Hui,Chen, Yanyan,Mo, Zuyu,Xu, Yanli,Yan, Yunyun,Zhang, Niuniu
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supporting information
p. 376 - 381
(2021/01/13)
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- Visible-light-promoted synthesis of secondary and tertiary thiocarbamates from thiosulfonates andN-substituted formamides
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A general visible-light-promoted metal-free synthesis of secondary and tertiary thiocarbamates starting from thiosulfonates andN-substituted formamides is developed. By employing rhodamine B as a photocatalyst andtert-butyl hydroperoxide (TBHP) as an oxidant, a wide scope of thiocarbamates can be obtained through direct thiolation of acyl C-H bonds under irradiation of blue light at room temperature for 12 h.
- Bi, Wen-Zhu,Zhang, Wen-Jie,Li, Zi-Jie,He, Yuan-Hao,Feng, Su-Xiang,Geng, Yang,Chen, Xiao-Lan,Qu, Ling-Bo
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supporting information
p. 8701 - 8705
(2021/10/22)
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- Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives
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A diverse chemoselective insertion reaction of sulfoxonium ylides and thiosulfonates under transition-metal-free conditions is developed, which successfully affords 1,4-diketone compounds, arylthiosulfoxide-ylides, and β-keto thiosulfones, respectively. The nucleophilic addition of two molecular sulfoxonium ylides to construct sulfone-substituted 1,4-dione compounds is the highlight of this work.
- Wang, Fei,Liu, Bo-Xi,Rao, Weidong,Wang, Shun-Yi
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p. 6600 - 6604
(2020/09/02)
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- Visible-light induced decarboxylative coupling of redox-active esters with disulfides to construct C-S bonds
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A novel method has been established for the construction of C-S bonds using redox-active esters with disulfides in the presence of Ru-photoredox catalyst. This method exhibits remarkable functional group tolerance across a wide scope of substrates. Under
- Xiao, Zhiwei,Wang, Lu,Wei, Junjie,Ran, Chongzhao,Liang, Steven H.,Shang, Jingjie,Chen, Guang-Ying,Zheng, Chao
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supporting information
p. 4164 - 4167
(2020/04/22)
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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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- Nickel-Catalyzed Defluorinative Reductive Cross-Coupling Reaction of gem-Difluoroalkenes with Thiosulfonate or Selenium Sulfonate
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A nickel-catalyzed defluorinative reductive cross-coupling of gem-difluoroalkenes with thiosulfonate or selenosulfonates is described. The reaction involves the formation of thiolated or selenylated monofluoroolefins via regioselective C-F bond cleavage and C-S or C-Se bond formation and features easily available substrates, mild reaction conditions, and high E-selectivity. One of the derivatives by further cross coupling with PhMgBr exhibited an aggregation-induced emission enhancement effect.
- Li, Jian,Rao, Weidong,Wang, Shun-Yi,Ji, Shun-Jun
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p. 11542 - 11552
(2019/09/30)
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- Unprecedented Reactivity of β-Iodovinyl Sulfones: An Efficient Synthesis of β-Keto Sulfones and β-Keto Thiosulfones
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An unprecedented reactivity of (E)-β-iodovinyl sulfones in the presence of NaOAc is reported. The (E)-β-iodovinyl sulfones were treated with NaOAc in DMSO/H2O to yield β-keto sulfones in moderate to high yields. A novel oxidative difunctionalization of β-iodovinyl sulfones with thiosulfonates and NaOAc in DMF has been developed. This metal-free oxosulfenylation is an operationally simple to access a wide range of β-keto thiosulfones (α-thioaryl-β-keto sulfones) in moderate to high yields. The transformations were reliable at gram-scale, thus illustrating its efficiency and practicality. A plausible mechanism for the protocol is also proposed.
- Reddy, Raju Jannapu,Kumar, Jangam Jagadesh,Kumari, Arram Haritha
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supporting information
p. 3771 - 3775
(2019/06/24)
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- Metal-Free Synthesis of Thiosulfonates via Insertion of Sulfur Dioxide
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A simple and catalyst-free strategy was developed for the synthesis of unsymmetrical thiosulfonates using readily available DABCO?(SO2)2 as a solid and bench-stable sulfur dioxide surrogate. The corresponding thiosulfonates were obtained through a radical pathway with good functional group tolerance. This strategy offers a promising synthesis method for the construction of diverse and useful thiosulfonates in the field of synthetic and pharmaceutical chemistry and extends the number of still limited sulfur dioxide fixation strategies. (Figure presented.).
- Li, Guoqing,Gan, Ziyu,Kong, Kexin,Dou, Xiaomeng,Yang, Daoshan
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supporting information
p. 1808 - 1814
(2019/03/28)
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- Method for synthesizing thiosulfonate compounds on the basis of strategy of SO2 insertion
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The invention relates to a method for synthesizing thiosulfonate compounds on the basis of strategy of SO2 insertion. The method includes: performing a reaction in the presence of nitrogen gas and atcertain temperature to prepare the thiosulfonate compoun
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Paragraph 0039; 0040; 0041; 0042; 0043
(2019/04/26)
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- Cs2CO3-Mediated Vicinal Thiosulfonylation of 1,1-Dibromo-1-Alkenes with Thiosulfonates: An Expedient Synthesis of (E)-1,2-Thiosulfonylethenes
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A new and highly efficient vicinal thiosulfonylation of 1,1-dibromo-1-alkenes with thiosulfonates in the presence of cesium carbonate has been developed. The metal-free diheterofunctionalization is an operationally simple to access a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields with high levels of stereoselectivities. Further, scalable reactions have been demonstrated for this transformation, thus illustrating its efficiency and practicality. (Figure presented.).
- Reddy, Raju Jannapu,Kumari, Arram Haritha,Kumar, Jangam Jagadesh,Nanubolu, Jagadeesh Babu
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supporting information
p. 1587 - 1591
(2019/02/16)
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- Gold/photoredox-cocatalyzed atom transfer thiosulfonylation of alkynes: Stereoselective synthesis of vinylsulfones
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We report a gold and photoredox combined radical approach for the rapid synthesis of thio-functionalized vinylsulfones from alkynes. Key features of this method include very mild conditions, broad substrate scope, excellent regio- and stereoselectivties, and 100% atom economy.
- Song, Tingting,Li, Haoyu,Wei, Fang,Tung, Chen-Ho,Xu, Zhenghu
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supporting information
p. 916 - 919
(2019/02/27)
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- Synthesis method of thiosulfonate compound
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The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of a thiosulfonate compound. The invention provides the synthesis method of the thiosulfonate compound. The method comprises the following steps that methanesulfonohydrazide compounds, thiophenol compounds, oxidizing agents and catalysts are dissolved into a solvent for reaction; purification isperformed to obtain the thiosulfonate compound; oxidizing agents are any one kind or several kinds of materials from tertiary butanol peroxide and catalysts are sodium iodide, potassium iodide, ammonium iodide, iodine element and tetrabutylammonium iodide. Through experiment testing, the thiosulfonate compound prepared by the technical scheme provided by the invention has the advantages that no side reaction occurs; the yield can reach 84 to 100 percent; the conversion rate is high; meanwhile, the used catalysts and catalysts are environment-friendly compounds; the environment pollution cannot be caused; the reaction temperature is low; the method is suitable for industrial mass popularization. The defects that in the prior art, the damage to the environment in the asymmetric thiosulfonates synthesis process is great, and the application to industrial production cannot be realized are overcome.
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Paragraph 0066-0070; 0072-0077; 0079-0084; 0086-0091; 0093
(2018/07/30)
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- Metal-free NaI/TBHP-mediated sulfonylation of thiols with sulfonyl hydrazides
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A highly efficient sulfonylation of thiols has been achieved through the metal-free NaI/TBHP-mediated cross-coupling of sulfonyl hydrazides and thiols at room temperature. This method provides a convenient and practical route to thiosulfonates in 84-99% y
- Chen, Qian,Huang, Yulin,Wang, Xiaofeng,Wu, Jiawei,Yu, Guodian
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p. 1713 - 1719
(2018/03/21)
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- Electrochemical sulfonylation of thiols with sulfonyl hydrazides: A metal- and oxidant-free protocol for the synthesis of thiosulfonates
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An efficient electrochemical transformation of structurally diverse sulfonyl hydrazides and thiols into thiosulfonates in the presence of ammonium iodide as redox catalyst and electrolyte in acetonitrile at ambient temperature is reported. Transition metal- and oxidant-free conditions are the striking features of this protocol. The in vitro cytotoxicity of all compounds is evaluated by MTT assay against four human cancer cell lines. The results reveal that 3ac and 3ag exhibit potential inhibitory activity against tumor cells. Furthermore, 3ag inhibits cell migration ability and tubulin polymerization in T-24 cells, leading to cell cycle arrest and apoptosis.
- Mo, Zu-Yu,Swaroop, Toreshettahally R.,Tong, Wei,Zhang, Yu-Zhen,Tang, Hai-Tao,Pan, Ying-Ming,Sun, Hong-Bin,Chen, Zhen-Feng
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supporting information
p. 4428 - 4432
(2018/10/17)
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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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- Visible-light-induced thiotrifluoromethylation of terminal alkenes with sodium triflinate and benzenesulfonothioates
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An unconventional reductive quenching cycle was developed to realize the visible-light-induced thiotrifluoromethylation of terminal alkenes. CF3SO2Na was used as an easy to handle CF3 radical source to afford the desired products in moderate to good yields. Mild reaction conditions and a broad substrate scope feature in this transformation.
- Kong, Weiguang,An, Hejun,Song, Qiuling
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supporting information
p. 8968 - 8971
(2017/08/15)
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- Iodide-Catalyzed Synthesis of Secondary Thiocarbamates from Isocyanides and Thiosulfonates
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A new method for the synthesis of secondary thiocarbamates from readily available isocyanides and thiosulfonates with broad functional group tolerance is reported. The reaction proceeds under mild reaction conditions in isopropanol and is catalyzed by inexpensive sodium iodide.
- Mampuys, Pieter,Zhu, Yanping,Sergeyev, Sergey,Ruijter, Eelco,Orru, Romano V. A.,Van Doorslaer, Sabine,Maes, Bert U. W.
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supporting information
p. 2808 - 2811
(2016/07/06)
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- Oxidative coupling of dichalcogenides with sodium sulfinates via copper-catalyzed cleavage of s-s and se-se bonds
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A copper-catalyzed sulfonylation of disulfides was achieved using sodium sulfinates in air. The reaction formed various sulfur-sulfone bonds efficiently and afforded thiosulfonates in good yields. Selenosulfonates could also be prepared with this procedure. Furthermore, both chalcogenide groups on the dichalcogenides were available in these reactions.
- Taniguchi, Nobukazu
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p. 1764 - 1770
(2015/02/19)
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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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- Hypervalent iodine in synthesis. XXII: A novel way for the preparation of unsymmetric S-aryl thiosulfonates by the reaction of potassium thiosulfonates with diaryliodonium salts
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Unsymmetric S-aryl thiosulfonates can be generated through a novel way for the reaction of potassium thiosulfonates with diaryliodonium salts in good yields under mild conditions.
- Xia, Min,Chen, Zhen-Chu
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p. 1309 - 1313
(2007/10/03)
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- THIOSULFONATE PREPARATION BY THE THIOSULFINATE/SULFINIC ACID REACTION
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The reaction of thiosulfinates with amine salts of aryl sulfinic acids has been examined for the preparation of thiosulfonates, particularly unsymmetrical derivatives.Key words: Thiosulfinate; thiosulfonate; sulfinic acid amine salts.
- Clarke, Victor,Cole, Edward R.
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p. 171 - 174
(2007/10/02)
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- INVESTIGATION OF THIOSULFONIC ACIDS. XXXIV. REACTION OF THIOSULFONIC ESTERS WITH SULFENAMIDES
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Thiosulfonic esters react with sulfenamides to form different thiosulfonic esters and sulfenamides.The process is only realized with initial esters having high reactivity and amides having high nucleophilicity, both significantly higher than the analogous characteristics of the final products.
- Boldyrev, B. G.,Bilozor, T. K.
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p. 1669 - 1671
(2007/10/02)
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- Selective Oxidation of Unsymmetrical Thiosulfinic S-Esters to the Corresponding Thiosulfonic S-Esters with NaIO4
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Unsymmetrical thiosulfinic S-esters were oxidized with sodium metaperiodate in aqueous media to the corresponding unsymmetrical thiosulfonic S-esters nearly quantitatively.The oxidation was accelerated by addition of a catalytic amount of inorganic and organic acids or halogen.Sulfinic esters were produced competitively along with the thiosulfonic S-esters in the oxidation of thiosulfinic S-esters in aqueous alcohol.However, unsymmetrical disulfides were not oxidized selectively to the corresponding unsymmetrical thiosufonic S-esters but a mixture of the both symmetrical and unsymmetrical thiosulfonic S-esters was obtained.
- Takata, Toshikazu,Kim, Yong Hae,Oae, Shigeru
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p. 1443 - 1447
(2007/10/02)
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