- 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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- Nickel-Catalyzed Difunctionalization of Alkynyl Bromides with Thiosulfonates and N -Arylthio Succinimides: A Convenient Synthesis of 1,2-Thiosulfonylethenes and 1,1-Dithioethenes
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An efficient nickel-catalyzed vicinal thiosulfonylation of 1-bromoalkynes with thiosulfonates in the presence of cesium carbonate is described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provides a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields. The extensive substrate scope of both alkynyl bromides and thiosulfonates is explored with a broad range of functional groups. Indole-derived 1,1-bromoalkenes were also successfully explored in this 1,2-thiosulfonylation process. Moreover, the nickel-catalyzed geminal -dithiolation of alkynyl bromides with N -arylthio succinimides provides 1,1-dithioalkenes in high yields. The present protocol is reliable on gram scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene is achieved in a scale-up synthesis. Following control experiments, a plausible mechanism is proposed to rationalize the experimental outcome and the vicinal thio-sulfonylation.
- Kumari, Arram Haritha,Kumar, Jangam Jagadesh,Krishna, Gamidi Rama,Reddy, Raju Jannapu
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supporting information
p. 2850 - 2864
(2021/05/18)
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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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- 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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- Phenylboronic acid-catalyzed tandem construction of S-S and C-S bonds: a new method for the synthesis of benzyl disulfanylsulfone derivatives fromS-benzyl thiosulfonates
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A unique phenylboronic acid-catalyzed dimerization-sulfonylation ofS-benzyl thiosulfonates has been disclosed. A metal-free tandem construction of S-S and C-S bonds is an operationally simple method to access a wide range of benzyl disulfanylsulfone derivatives in high to excellent yields. Moreover, the robustness of this tandem transformation has been demonstrated by gram-scale reactions, and a plausible mechanism is also proposed.
- Jannapu Reddy, Raju,Rama Krishna, Gamidi,Waheed, Md.
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supporting information
p. 3243 - 3248
(2020/05/14)
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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 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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- Copper-Catalyzed Oxidative Trifunctionalization of Olefins: An Access to Functionalized β-Keto Thiosulfones
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Aerobic oxidative trifunctionalization of olefins for the synthesis of functionalized β-keto thiosulfones has been described. The transformation proceeds through molecular oxygen activation under copper catalysis and forms the two new C-S bonds in a single operation using mild conditions. A novel Cu-catalyzed sulfonyl radical addition/oxidation/funtionalization relay mechanism was proposed for the discovered reaction.
- Huang, Shuai,Thirupathi, Nuligonda,Tung, Chen-Ho,Xu, Zhenghu
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p. 9449 - 9455
(2018/08/01)
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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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- An odorless, one-pot synthesis of thioesters from organic halides, thiourea and benzoyl chlorides in water
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Thioesterification can be realized via an odorless, one-pot reaction through the in situ generation of S-alkylisothiouronium salts from organic halides and thiourea in aqueous Triton X-100 (TX100) micelles. The protocol is free of foul-smell thiols and or
- Lu, Guo-Ping,Cai, Chun
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supporting information
p. 1271 - 1276
(2013/06/26)
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- Sc(OTf)3-catalyzed synthesis of thiosulfonates in ionic liquid-water
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The first example of Sc(OTf)3-catalyzed sulfenylation of sodium sulfinates with N-(organothio)succinimides in ionic liquids (ILs) and water cosolvent system was developed, achieving thiosulfonates in moderate to excellent yields. Additionally, Sc(OTf)3/ILs could be recovered easily after the reactions and reused without a significant loss in the catalytic activity. Thus, the present protocol represents an interesting complement to known methods for thiosulfonates synthesis.
- Liang, Gaigai,Chen, Jing,Chen, Jiali,Li, Wanmei,Chen, Jiuxi,Wu, Huayue
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supporting information
p. 6768 - 6770
(2013/01/15)
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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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- Functionalized benzylic magnesium reagents through a sulfur-magnesium exchange
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(Chemical Equation Presented) Switch it: lodobiphenyl thioethers readily undergo an iodine-magnesium exchange followed by, after the addition of tBuOLi, an intramolecular sulfur-magnesium exchange, which provides benzylic magnesium reagents in excellent yield through a fragmentation reaction.
- Stoll, Armin H.,Krasovskiy, Arkady,Knochel, Paul
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p. 606 - 609
(2007/10/03)
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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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- A new route to thio- and selenosulfonates from disulfides and diselenides. Application to the synthesis of new thio- and selenoesters of triflic acid
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Alkyl and aryl trifluoromethanethiosulfonates1 (or selenosulfonates) were prepared in one step either from alkyl and aryl sulfenyl (or selenenyl) chlorides and sodium trifluoromethanesulfinate (3) or, more generally, from disulfides (or diselenides), 3, and bromine. The second method involved trifluoromethanesulfonyl bromide as key intermediate. Benzenethiosulfonates were obtained in a similar way from disulfides, benzenesulfinate, and bromine but benzeneselenosulfonates could not be obtained by the same method from diselenides.
- Billard, Thierry,Langlois, Bernard R.,Large, Sylvie,Anker, Daniel,Roidot, Nathalie,Roure, Philippe
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p. 7545 - 7550
(2007/10/03)
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- N3-(ARYLTHIO-, ARALKYLTHIO- AND ALKYLTHIO)-5,5-DIMETHYLHYDANTOINS: SULFENYL GROUP TRANSFER REACTIONS AND THEIR PROPERTIES
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Sulfenyl-transfer reactions toward a variety of nucleophiles were successfully carried out using N3-sulfenyl-substituted 5,5-dimethylhydantoins (2a-c).During the course of the synthesis of 2 by the reaction of N1-bromo-5,5-dimethylhydantoin (1c) with disulfides, the sulfenyl groups were found to be at the position of N3 although the bromine was at N1 in the starting monobromohydantoin (1c).Some mechanistic speculations were considered for the formation of 2 from 1c.
- Takeda, Ken'ichi,Horiki, Kusuo
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p. 367 - 373
(2007/10/02)
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