- (Thio)etherification of Quinoxalinones under Visible-Light Photoredox Catalysis
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An efficient visible-light-induced (thio)etherification of quinoxalin-2(1H)-ones with divergent aliphatic alcohols and thiols (primary, secondary, and tertiary) at room temperature in air has been developed. This protocol was highlighted by its mild conditions, readily available starting materials, operational simplicity, and wide functional group tolerance. (Figure presented.).
- Zhou, Jiadi,Zhou, Peng,Zhao, Tingting,Ren, Quanlei,Li, Jianjun
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- Oxidation of bis-sulfinyl carbanions as the pivot of ionic/radical tandem reactions
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[1,4]-additions of various nucleophiles such as lithiated carbamates, alkoxides or ester enolates onto enantiopure alkylidene bis-sulfoxides proceed with high diastereoselectivity. The oxidation of the resulting carbanions with iron(III) salts induces the
- Vincent, Guillaume,Cheli, Saloua,Martinez Mallorquin, Rocio,Abramovitch, Adi,Beauvière, Sophie,Gomez, Catherine,Brebion, Franck,Marek, Ilan,Malacria, Max,Goddard, Jean Philippe,Fensterbank, Louis
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- Facile Conversion of Thiosulfinic S-Ester to Sulfinic Ester
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Thiosulfinic S-esters are readily converted to the corresponding sulfinic esters in good yields by treating in alcohols with a catalytic amount of I2, Br2, or HCl in the presence of H2O2, replacing sulfenyl groups by alcohols.The mechanism of this reaction is also discussed.
- Takata, Toshikazu,Oae, Shigeru
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- Second monoclinic polymorph of S-(4-tolyl) 4-toluenethiosulfonate at 150 and 293 K
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The structure of S-(4-tolyl) 4-toluenethiosulfonate is described at 150 and 293 K. The compound does not contain intermolecular C-H···O hydrogen bonds. Compared to another polymorph, the compound's crystal structure have effective acceptors in the form of
- Ferguson, George,Glidewell, Christopher,Low, John Nicolson,Wardell, James L.
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- Vibrational and NMR spectroscopic studies of a thiolsulphonate produced from the non-catalytic hydrogenation of polybutadiene
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Mass spectrometry, 1H NMR, 13C NMR, 2D NMR, FT-IR and Raman spectroscopy have been used to established the structure of a thiosulphonate by-product in the non-catalytic hydrogenation process for polybutadiene, which makes use of p-toluene sulphonylhydrazi
- Edwards, H. G. M.,Johnson, A. F.,Lewis, I. R.,Maitland, D. J.,Webb, N.
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- Reaction of primary thioamides with p-toluenesulfinic acid
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The conversion of thioamides to the corresponding 1,2,4-thiadiazoles occurs upon heating primary thioamides with formaldehyde and p-toluenesulfinic acid in water instead of the formation of N-(tosylmethyl)thioamides. 1997 Plenum Publishing Corporation.
- Shutalev,Kishko,Alekseeva
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- Oxidation of Symmetric Disulfides with Hydrogen Peroxide Catalyzed by Methyltrioxorhenium(VII)
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Organic disulfides with both alkyl and aryl substituents are oxidized by hydrogen peroxide when CH3ReO3 (MTO) is used as a catalyst. The first step of the reaction is complete usually in about an hour, at which point the thiosulfinate, RS(O)SR, can be detected in nearly quantitative yield. The thiosulfinate is then converted, also by MTO-catalyzed oxidation under these conditions, to the thiosulfonate and, over long periods, to sulfonic acids, RSO3H. In the absence of excess peroxide, RS(O)SR (R = p-tolyl), underwent disproportionation to RS(O)2SR and RSSR. Kinetics studies of the first oxidation reaction established that two peroxorhenium compounds are the active forms of the catalyst, CH3ReO2(η2-O2) (A) and CH3ReO(η2-O2)2·(OH 2) (B). Their reactivities are similar; typical rate constants (L mol-1 s-1, 25°C, aqueous acetonitrile) are kA = 22, kB = 150 (Bu2S2) and kA = 1.4, kB = 11 (Tol2S2). An analysis of the data for (P-XC6H4)2S2 by a plot of log kB against the Hammett σ constant gave ρ = -1.89, supporting a mechanism in which the electron-rich sulfur attacks a peroxo oxygen of intermediates A and B.
- Wang, Ying,Espenson, James H.
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- Tetrabutylammonium Iodide Mediated Sulfenylation of Poly-substituted 1 H -Pyrazol-5-amines with Arylsulfonyl Hydrazides
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A TBAI-mediated sulfenylation of N,3-diaryl-1-arylsulfonyl-1H-pyrazol-5-amines with arylsulfonyl hydrazides has been established, and an expanded inventory of N,5-diaryl-4-(arylthio)-1H-pyrazol-3-amines was constructed through C-S bond formation and N-S bond breaking. Mechanistic investigations suggest thiosulfonate as a key intermediate in the sulfenylation, and the detosylation is promoted by the generated arylsulfinic acid. The method is characterized by simple operating conditions, broad substrate range as well as gramscale reaction.
- He, Jing,Wei, Yueting,Li, Xuezhen,Dai, Bin,Liu, Ping
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p. 490 - 498
(2021/10/21)
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- Synthesis of Symmetrical and Unsymmetrical Thiosulfonates from Disulfides through Electrochemically Induced Disulfide Bond Metathesis and Site-Selective Oxidation
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The anodic generation of symmetrical and unsymmetrical thiosulfonates is presented. First, the oxidation of disulfides yielding symmetrical thiosulfonates was realized. The direct synthesis is performed using a simple quasi-divided cell design, whereby using a supporting electrolyte is unnecessary. Its principle was then expanded to the conversion of unsymmetrical disulfides that were generated in situ through metathesis of two symmetrical disulfides. This enables a direct access to unsymmetrical thiosulfonates without any pre-functionalization or elaborate synthesis of the starting materials for the first time. The reaction scope was investigated by converting differently functionalized aliphatic and aromatic disulfides in moderate to very good yields. Furthermore, a sensitivity assessment for an improved reproducibility and a robustness screen to determine the compatibility of the reaction against functional groups were performed.
- Strehl, Julia,Hilt, Gerhard
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supporting information
(2021/10/14)
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- Deoxygenative C-S Bond Coupling with Sulfinates via Nickel/Photoredox Dual Catalysis
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The C-S bond formation from aryl halides and thiols has been well established under various catalytic systems. In this work, user-friendly sulfinates have been exploited as an efficient sulfenylating reagent in the C-S couplings through visible-light-induced photo/nickel dual catalysis under base- and external reductant-free conditions. A large number of aryl sulfide products were accessed with high selectivity and high tolerance of various functionalities.
- Deng, Guo-Jun,Huang, Huawen,Mao, Guojiang,Zhao, Feng,Zhong, Shuai,Zhou, Zhiwei
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supporting information
p. 1865 - 1870
(2022/03/16)
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- Synthesis of symmetrical / unsymmetrical thiosulfonates through the disproportionate coupling reaction of sulfonyl hydrazide mediated by phosphomolybdic acid
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Phosphomolybdic acid (H3PMo12O40) is reported as a green low-cost catalyst for the synthesis of symmetrical / unsymmetrical thiosulfonates via the disproportionate coupling reaction of sulfonyl hydrazide. The attributes of this reported catalytic system include low catalyst loadings (1 mol%), efficient turnover, and high yields (up to 94%). Additionally, this reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via sulfinyl radical disproportionation.
- Lv, Mengting,Liu, Yufeng,Li, Ke,Yang, Guoping
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supporting information
(2021/01/21)
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- Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides
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A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO 2·CH 2O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing-coupling pathway.
- Zhang, Guofu,Fan, Qiankun,Zhao, Yiyong,Wang, Huimin,Ding, Chengrong
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supporting information
p. 81 - 85
(2020/11/03)
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- Controllable Activation of β-Alkyl Nitroalkenes: Regioselective Synthesis of Allyl and Vinyl Sulfones
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The regiospecific radical reactions of β-alkyl nitroalkenes with sulfonyl hydrazides depended to a great extent on the choice of a solvent and catalyst. In the presence of dimethylformamide (DMF), β-alkyl nitroalkenes more likely converted into electron-rich allyl nitro compounds, which reacted with sulfonyl hydrazides to afford allyl sulfones with high regioselectivity. While in acetonitrile (CH3CN), vinyl sulfones were obtained directly via sulfonation of electron-deficient β-alkyl nitroalkenes. The mechanism investigation revealed that the regioselectivity was controlled by the equilibrium of β-alkyl nitroalkenes and allyl nitro compounds.
- Wang, Ye,Xiong, Guowei,Zhang, Chuanxin,Chen, Yunfeng
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p. 4018 - 4026
(2021/03/01)
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- Electrochemical cross-coupling reactions of sodium arenesulfinates with thiophenols and phenols
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A green electrochemical oxidative cross-coupling protocol for the generation of thiosulfonates and sulfonate esters using sodium arenesulfinates and thiophenols/phenols is disclosed. The protocol involves using inorganic and non-toxic NaI as both redox catalyst and supporting electrolyte at room temperature without oxidant and base. The reactions provide good yields of products and tolerate broad substrate scope. The mechanistic studies revealed that the reactions proceed via a radical pathway for the formation of SO2–S and SO2–O bonds.
- Zhong, Zijian,Xu, Pan,Ma, Jinfeng,Zhou, Aihua
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supporting information
(2021/10/26)
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- Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides
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A novel strategy for the synthesis of sulfides and selenides from phosphonium salts and thio- or selenesulfonates, commercially available compounds, is described. When phosphoranes were used in the reaction, different products were obtained. The methodology does not require the use of metals, reactive species, or anhydrous conditions to be performed.
- Moura, Igor M. R.,Tranquilino, Arisson,Sátiro, Barbara G.,Silva, Ricardo O.,De Oliveira-Silva, Diogo,Oliveira, Roberta A.,Menezes, Paulo H.
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p. 5954 - 5964
(2021/05/04)
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- Paired Electrolysis Enabled Ni-Catalyzed Unconventional Cascade Reductive Thiolation Using Sulfinates
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Herein, we have reported a nickel-catalyzed cascade reductive thiolation of aryl halides with sulfinates driven by paired electrolysis. This protocol uses sulfinates as the sulfur source, and various thioethers could be synthesized under mild conditions. By mechanism exploration, we find that a cascade chemical step is allowed on the electrode interface and could alter the reaction pathway in paired electrolysis, whose findings could help the discovery of novel cascade reactions with unique reactivity.
- Kang, Jun-Chen,Li, Zi-Hao,Chen, Chao,Dong, Li-Kun,Zhang, Shu-Yu
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supporting information
p. 15326 - 15334
(2021/10/25)
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- Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
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Direct conversion of sulfinamides to thiosulfonates is described. Without the use of additional redox agents, the reaction proceeds smoothly in the presence of TFA under metal-free conditions. This protocol possesses many advantages such as odourless and stable starting materials, broad substrate scope, selective synthesis, and mild reaction conditions. This journal is
- Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
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p. 9291 - 9298
(2021/11/13)
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- Copper-Catalyzed N-Directed Distal C(sp3)-H Sulfonylation and Thiolation with Sulfinate Salts
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We herein report a selective and catalytic C(sp3)-H functionalization approach to access amines bearing organo-sulfonyl and organo-thiol groups. This reaction proceeds through a cascade process of N-radical formation, alkyl radical formation via 1,5-HAT, and C-S bond formation, thereby offering a series of functionalized amines. This method could enable primary, secondary, and tertiary C(sp3)-H sulfonylation and thiolation and also exhibits good functional group tolerance.
- Chen, Guang-Le,He, Shi-Hui,Cheng, Liang,Liu, Feng
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supporting information
p. 8338 - 8342
(2021/10/25)
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- Temperature-Controlled Chemoselective Synthesis of Thiosulfonates and Thiocyanates: Novel Reactivity of KXCN (X=S, Se) towards Organosulfonyl Chlorides
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An efficient chemoselective protocol has been developed for the synthesis of thiosulfonates and thiocyanates by employing cost effective and commercially available organosulfonyl chlorides with potassium thio-/selenocyanate. The strategy offered the thiosulfonates and thiocyanates selectively by tuning the equivalents of KSeCN and optimizing the reaction temperature. On the other hand, thiosulfonates were obtained as sole products when organosulfonyl chlorides were treated with KSCN. Furthermore, the syntheses of diarylthioethers and aryl(heteroaryl) thioethers were carried out as a part of synthetic application of newly prepared arylthiocyanates.
- Kalaramna, Pratibha,Goswami, Avijit
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supporting information
p. 5359 - 5366
(2021/10/25)
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- Synthesis of Symmetrical Thiosulfonates via Cu(OTf)2-Catalyzed Reductive Homocoupling of Arenesulfonyl Chlorides
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A variety of symmetrical thiosulfonates are synthesized via Cu-catalyzed reductive homocoupling of aryl sulfonyl chlorides. This protocol uses organic amine acting as a mild reductant and low-cost copper as an effective catalyst. Such a reductive coupling process features a broad substrate scope and good functional group tolerance. Related thiosulfonate products can also be converted into diverse functional molecules.
- Liu, Lixia,Luo, Bo,Wang, Chengming
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supporting information
p. 5880 - 5883
(2021/11/27)
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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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- 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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- 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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- 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 0016; 0081-0085
(2021/05/19)
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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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- H4SiW12O40-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides: An efficient synthesis of 3,4-disubstituted 1H-pyrazoles
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A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H4SiW12O40)-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides/aldehydes were smoothly reacted with sulfonyl hydrazides to furnish regioselectivity 3,4-disubstituted 1H-pyrazoles. The application of such an earth-abundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of 3,4-disubstituted 1H-pyrazoles. A plausible reaction mechanism has been proposed on the basis of control experiments, GC-MS and DFT calculations.
- Cheng, Mengyuan,Cheng, Yuanyuan,Gao, Xiaofei,Li, Ke,Lin, Xiaoling,Liu, Yufeng,Xie, Xuanjie,Yang, Guoping
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supporting information
(2021/09/06)
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- CuCl2-promoted decomposition of sulfonyl hydrazides for the synthesis of thiosulfonates
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Sulfonyl hydrazides recently received much attention as reagents for the introduction of sulfur-containing functional groups into organic compounds, because both sulfonyl and sulfenyl sources could be generated by the oxidation and decomposition of the sulfonyl hydrazides, respectively. However, the transformations of sulfonyl hydrazides into thiosulfonates, which could be produced by the reaction between sulfonyl and sulfenyl sources, have been less investigated. In this manuscript, we describe CuCl2-promoted selective synthesis of thiosulfonates from sulfonyl hydrazides. A variety of thiosulfonates were produced in moderate to good yields. The mechanism involving radical intermediates such as sulfonyl radical and thiyl radical was proposed on the basis of the previously reported references and mechanistic investigations. In addition, quantum chemical simulations revealed that Cu-promoted decomposition of sulfonyl hydrazides is thermodynamically viable in the developed conditions.
- Kim, Junsu,Park, Sanggil,Kim, Hyungjun,Kim, Jinho
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supporting information
(2020/07/02)
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- Microwave-assisted and catalyst-free sulfenylation of imidazo[2,1-b]thiazoles with sulfonyl hydrazides in water
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An efficient microwave-assisted and catalyst-free sulfenylation of imidazo[2,1-b]thiazoles with sulfonyl hydrazides has been developed in water. This method is practical and environmental friendly, and can be performed within a short reaction time. The sulfenylation reaction shows high regioselectivity, and excellent functional-group compatibility, giving the desired products in moderate to good yields.
- Wang, Shaohua,Luo, Run,Guo, Lina,Zhu, Tianxi,Chen, Xu,Liu, Wenjie
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p. 805 - 811
(2020/07/03)
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- An Alternative Metal-Free Aerobic Oxidative Cross-Dehydrogenative Coupling of Sulfonyl Hydrazides with Secondary Phosphine Oxides
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An alternative metal-free, efficient and practical approach for the preparation of phosphinothioates is established via the aerobic oxidative cross-dehydrogenative coupling (CDC) of sulfonyl hydrazides with secondary phosphine oxides catalyzed by tetrabutylammonium iodide (TBAI) in the presence of atmospheric oxygen. The strategy provides an array of diverse phosphinothioates in good to excellent yields. Furthermore, two representative bioactive molecules are synthesized on up to gram scale by utilizing this method.
- Cheng, Feixiang,Liu, Jianjun,Liu, Teng,Yu, Rong,Zhang, Yanqiong
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p. 253 - 262
(2019/12/28)
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- Silver-promoted oxidative sulfonylation and ring-expansion of vinylcyclopropanes with sodium sulfinates leading to dihydronaphthalene derivatives
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Silver-promoted sulfonylation and ring-expansion of vinylcyclopropanes with sodium sulfinates is established for the construction of 1-sulfonylmethylated 3,4-dihydronaphthalenes. This sulfonylation process involves a radical pathway, including sulfonyl radical formation, radical addition, ring-opening and cyclization. The 1-sulfonylmethylated 3,4-dihydronaphthalenes can be converted into other useful products.
- Chen, Pu,Chen, Zan,Liang, Yun,Liu, Yu,Liu, Yu-Kui,Tang, Ke-Wen,Zhou, Quan
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supporting information
p. 7345 - 7354
(2020/10/13)
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- Alkene: Versus alkyne reactivity in unactivated 1,6-enynes: Regio-And chemoselective radical cyclization with chalcogens under metal-And oxidant-free conditions
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Herein, we have developed metal and oxidant-free visible light-promoted alkene vs. alkyne regio-And chemoselective radical cascade cyclization of electronically unbiased 1,6-enynes with chalcogens to synthesize substituted pyrrolidines bearing chalcogens. The reaction generated three new bonds, namely, C-SO2, C-C, and C-Se under extremely mild conditions. Furthermore, we achieved regio-And chemoselective mono-addition of aromatic thiophenols with unactivated 1,6-enynes. The key features of this protocol are broad substrate scope, environment-friendly conditions, operational simplicity, atom economy, and amenability to gram-scale synthesis. The mechanistic studies corroborate that the reaction proceeds via a radical pathway.
- Kudale, Vishal Suresh,Li, Jing,Mutra, Mohana Reddy,Tsai, Wu-Hsun,Wang, Jeh-Jeng
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supporting information
p. 2288 - 2300
(2020/04/21)
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- S-(4-Methoxyphenyl)-4-methoxybenzenesulfonothioate as a Promising Lead Compound for the Development of a Renal Carcinoma Agent
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Organosulfur compounds show cytotoxic potential towards many tumor cell lines. Disulfides and thiosulfonates act through apoptotic processes, inducing proteins associated with apoptosis, endoplasmic reticulum stress, and the unfolded protein response. Three p-substituted symmetric diaryl disulfides and three diaryl thiosulfonates were synthesized and analyzed for inhibition of tubulin polymerization and for human cancer cell cytotoxic activity against seven tumor cell lines and a non-tumor cell line. S-(4-methoxyphenyl)-4-methoxybenzenesulfonothioate (6) exhibited inhibition of tubulin polymerization and showed the best antiproliferative potential, especially against the 786-0 cell line, being six times more selective as compared with the non-tumor cell line. In addition, compound 6 was able to activate caspase-3 after 24 and 48 h treatments of the 786-0 cell line and induced cell-cycle arrest in the G2/M stage at the highest concentration evaluated at 24 and 48 h. Compound 6 was able to cause complete inhibition of proliferation, inducing the death of 786-0 cells, by increasing the number of cells at G2/M and greater activation of caspase-3.
- Nantes, Camilla I.,Pereira, Ingrid D.,Bai, Ruoli,Hamel, Ernest,Burnett, James C.,de Oliveira, Rodrigo J.,de F. C. Matos, Maria,Beatriz, Adilson,Yonekawa, Murilo K. A.,Perdomo, Renata T.,de Lima, Dênis P.,Bogo, Danielle,dos A. dos Santos, Edson
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p. 449 - 458
(2020/01/25)
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- Perfluoroalkylation of Thiosulfonates: Synthesis of Perfluoroalkyl Sulfides
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A practical synthesis of perfluoroalkyl sulfides is described. The method employs stable and readily accessible thiosulfonates as new electrophiles with commercial nucleophilic perfluoroalkylating reagents. The mild reaction conditions allow access to a wide variety of both aryl- and alkyl-substituted perfluoroalkyl sulfides amenable to pharmaceutical development. Furthermore, the reaction operation is straightforward, odorless, does not produce toxic wastes, and, therefore should appeal to practitioners in industrial-scale productions.
- Luo, Ziwei,Yang, Xinkan,Tsui, Gavin Chit
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supporting information
p. 6155 - 6159
(2020/07/30)
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- Diastereoselective Synthesis of Z-Alkenyl Disulfides from α-Thiophosphorylated Ketones and Thiosulfonates
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We developed a simple and efficient method for the synthesis of functionalized unsymmetrical Z-alkenyl disulfides under mild conditions in moderate to good yields. The designed method is based on the reaction of α-thiophosphorylated carbonyl compounds with thiotosylates in the presence of a base. The developed method allows the preparation of unsymmetrical Z-alkenyl disulfides bearing additional hydroxy, carboxy, or ester functionalities. (Figure presented.).
- Musiejuk, Mateusz,Doroszuk, Justyna,J?drzejewski, Bartosz,Ortiz Nieto, Gregory,Marin Navarro, Marisol,Witt, Dariusz
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supporting information
p. 618 - 626
(2019/12/24)
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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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- Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
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A magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of diaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. Sulfones containing molecules have medicinal relevance as they are known to possess various activities such as antifungal, anti-HIV, antitumor, and anticancer. Herein, a magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of biaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. In this newly developed protocol TosMIC acts as sulfonyl source. The catalyst can magnetically be recovered and recycled five times without significant loss in activity.
- Phanindrudu, Mandalaparthi,Jaya, Pogula,Likhar, Pravin R.,Tiwari, Dharmendra Kumar
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- Electrochemical synthesis of sulfonamides in a graphite powder macroelectrode
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The electrochemical generation of sulfinyl radicals from commercially available and non-expensive sodium salts of sulfinic acids is described. Electrooxidation reactions were carried out in a graphite powder macroelectrode using an aqueous electrolyte and cavity cell. Further reaction with primary or secondary amines gave the corresponding sulfonamides, a unit present in several biologically active compounds and pharmaceuticals, in good yields.
- Galdino, Danilo,Menezes, Paulo H.,Navarro, Marcelo,Vicente, Dmistocles A.
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p. 5262 - 5266
(2020/09/17)
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- Preparation method of thiosulfonate compounds in aqueous phase
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The invention relates to a preparation method of thiosulfonate compounds in an aqueous phase. The preparation method comprises adding sulfonyl hydrazide, an accelerant, an oxidant and solvent water into a Schlenk reaction bottle, stirring to allow to react under certain temperature and air atmosphere, and carrying out free radical coupling reaction to obtain the thiosulfonate compounds.
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Paragraph 0027-0052
(2019/06/27)
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- Radical Heck-type reaction of styrenes with sulfonyl hydrazides on water at room temperature
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Herein, metal-free radical Heck-type reaction of styrenes with sulfonyl hydrazides to synthesize vinyl sulfones is developed. The reaction is performed under economical TBAI/TBHP system on water in open air at room temperature, which proceeds through the
- Bao, Wen-Hui,Ying, Wei-Wei,Xu, Xu-Dong,Zhou, Guo-Dong,Meng, Xiao-Xiao,Wei, Wen-Ting,Liu, Yan-Yun,Li, Qiang
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supporting information
p. 55 - 58
(2018/11/30)
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- Solvent Controlled Transformation between Sulfonyl Hydrazides and Alkynes: Divergent Synthesis of Benzo[b]thiophene-1,1-dioxides and (E)-β-iodo Vinylsulfones
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A green, efficient and controllable transformation between sulfonyl hydrazides and alkynes leading to benzo[b]thiophene-1,1-dioxides and (E)-β-iodo vinylsulfones via radical pathway has been developed. The reaction occurs rapidly in the presence of simply H2O2 and KI without the help of any transition metal. The chemoselectivity of the reaction is determined by the solvent in which the process is performed: TFE favors the cyclic product, while H2O medium generates the iodosulfonylative product. Notably, this protocol also represents the first direct approach to the aggregation-induced-emmision (AIE) active benzo[b]thiophene-1,1-dioxides from readily available sulfonyl hydrazides and alkynes in one step. (Figure presented.).
- Ma, Yue,Wang, Kun,Zhang, Dong,Sun, Peng
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p. 597 - 602
(2018/12/13)
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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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- 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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supporting information
p. 3204 - 3209
(2019/05/01)
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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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- 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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- Visible-Light-Catalyzed C-C Bond Difunctionalization of Methylenecyclopropanes with Sulfonyl Chlorides for the Synthesis of 3-Sulfonyl-1,2-dihydronaphthalenes
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A novel visible-light-catalyzed sulfonylation/arylation of carbon-carbon σ-bond with sulfonyl chlorides for the synthesis of 3-sulfonylated 1,2-dihydronaphthalenes is developed. This difunctionalization proceeds via a sequence of C=C bond sulfonylation, C-C σ-bond cleavage, and intramolecular cyclization, and the experiment result shows that the C-C σ-bond difunctionalization reaction includes a radical process. This strategy provides a simple and convenient route for difunctionalization of C-C bonds with an aromatic carbon and a sulfonyl radical by one-pot construction of a C-S bond and a new C-C bond.
- Liu, Yu,Wang, Qiao-Lin,Chen, Zan,Zhou, Quan,Li, Hua,Zhou, Cong-Shan,Xiong, Bi-Quan,Zhang, Pan-Liang,Tang, Ke-Wen
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p. 2829 - 2839
(2019/03/07)
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- Ammonium iodide-mediated electrosynthesis of unsymmetrical thiosulfonates from arenesulfonohydrazides and thiols
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Unsymmetrical thiosulfonates were synthesized from thiols and arenesulfonohydrazides by their electrolysis in undivided cell equipped with graphite anode and stainless steel cathode under high current density applying NH4I both as a redox catal
- Terent'ev, Alexander O.,Mulina, Olga M.,Ilovaisky, Alexey I.,Kokorekin, Vladimir A.,Nikishin, Gennady I.
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- Silver-mediated oxidative C-C bond sulfonylation/arylation of methylenecyclopropanes with sodium sulfinates: facile access to 3-sulfonyl-1,2-dihydronaphthalenes
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The novel AgNO3-mediated oxidative sulfonylation/arylation of a C-C σ-bond in methylenecyclopropanes with sodium sulfinates to synthesize various 3-sulfonylated 1,2-dihydronaphthalenes is reported. This sulfonylation/arylation transformation proceeds via a sequence of sulfonylation, C-C σ-bond cleavage and intramolecular cyclization, and the experimental results show that the C-C σ-bond difunctionalization reaction includes a radical process. This strategy provides a simple and convenient route for the difunctionalization of C-C bonds with a phenyl ring and a sulfonyl radical via the one-pot construction of a C-S bond and a new C-C bond.
- Liu, Yu,Wang, Qiao-Lin,Chen, Zan,Zhou, Quan,Zhou, Cong-Shan,Xiong, Bi-Quan,Zhang, Pan-Liang,Yang, Chang-An,Tang, Ke-Wen
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supporting information
p. 1365 - 1369
(2019/02/14)
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- Transition Metal-Free Difunctionalization of C?C Bond with Sodium Sulfinates and Water Leading to (E)-1-Phenyl-4-sulfonylbut-1-enes
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Without using any transitionmetal and base, an eco-friendly, practical and economical protocol has been established for the one-pot synthesis of diverse (E)-1-phenyl-4-sulfonylbut-1-enes from easily accessible starting materials. This strategy features a wide substrate scope, tolerates a broad range of functional groups, employs a less expensive oxidant, is operationally simple, and can be easily scaled-up. (Figure presented.).
- Wang, Qiao-Lin,Chen, Zan,Zhou, Quan,Zhou, Cong-Shan,Xiong, Bi-Quan,Zhang, Pan-Liang,Yang, Chang-An,Liu, Yu,Tang, Ke-Wen
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supporting information
p. 2315 - 2320
(2019/04/13)
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- Transition-Metal-Free Synthesis of Thiosulfonates through Radical Coupling Reaction
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An efficient and practical transition-metal-free radical coupling reaction of sulfonyl hydrazides mediated by NIS/K 2 S 2 O 8 has been developed to afford a variety of biological activity thiosulfonates in moderate to excellent yields. Compared to a known approach for the synthesis of thiosulfonates from sulfonyl hydrazides, this strategy features high yields, mild reaction conditions, and broad substrate scope. The mechanistic studies revealed that the procedure undergoes via a radical cross-coupling process for the construction of S-S bonds.
- Zhou, Guodong,Xu, Xu-Dong,Chen, Gan-Ping,Wei, Wen-Ting,Guo, Zhiyong
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supporting information
p. 2076 - 2080
(2018/09/18)
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- The fast and efficient KI/H2O2 mediated 2-sulfonylation of indoles and N-methylpyrrole in water
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The rapid and efficient KI/H2O2-mediated 2-sulfonylation of substituted indoles and N-methylpyrrole was established. The corresponding 2-sulfonylation products are synthesized from readily available sulfur sources, namely arylsulfonyl hydrazides, 4-methylbenzenesulfinic acid and sodium 4-methylbenzenesulfinate in good to excellent yields in only 5 min. Moreover, the aqueous solution of hydrogen peroxide is used as both oxidant and solvent. Mechanistic studies demonstrated that 2,3-diiodoindoline was the main sulfonylation intermediate.
- Zhang, Jun,Wang, Zhong,Chen, Lingjuan,Liu, Yan,Liu, Ping,Dai, Bin
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p. 41651 - 41656
(2019/01/03)
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- Cu-catalyzed direct C-H thiolation of electron-rich arenes with arylsulfonyl hydrazides
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An efficient Cu-catalyzed direct C–H thiolation of electron-rich arenes with arylsulfonyl hydrazides has been developed. Various mono(or bis)-thioether products were obtained in moderate to good yields. Mechanistic studies suggest that the reaction likely proceeds through free-radical formation including arylthio radical and sulfonyl radical, while both disulfanes and sulfonothioates are the major thiolation species in this transformation.
- Chen, Lingjuan,Liu, Ping,Wu, Jianglong,Dai, Bin
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p. 1513 - 1519
(2018/02/21)
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- Cu-catalysed direct bis-thiolation of benzoheterocycles with arylsulfonyl hydrazides
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A series of bis-arylsulfenylated indoles (10), benzofurans (3), and benzothiophenes (3) and of monosulfenylated indoles (5), 12 of which are novel, were prepared in good yields via a Cu-catalysed direct sulfenylation of benzoheterocycles with arylsulfonyl hydrazides. Sulfonothioates are probably the major thiolated intermediates in this transformation.
- Chen, Lingjuan,Pu, Jiangxin,Liu, Ping,Dai, Bin
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p. 456 - 462
(2018/10/15)
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- Disproportionate Coupling Reaction of Sodium Sulfinates Mediated by BF3·OEt2: An Approach to Symmetrical/Unsymmetrical Thiosulfonates
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The BF3·OEt2-mediated disproportionate coupling reaction of sodium sulfinates was found for the first time. In this reaction, various S-S(O)2 bonds can be formed, efficiently giving thiosulfonates in moderate to excellent yields. As a convenient protocol for the synthesis of symmetrical and unsymmetrical thiosulfonates, its reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via a sulfinyl radical disproportionation. What is more, this transformation can also be applied practically as a gram-scale reaction and to the two-step synthesis of sulfone and sulfonamide in one pot in situ using thiosulfonate as an intermediate.
- Cao, Liang,Luo, Shi-He,Jiang, Kai,Hao, Zhi-Feng,Wang, Bo-Wen,Pang, Chu-Ming,Wang, Zhao-Yang
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supporting information
p. 4754 - 4758
(2018/08/24)
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- Synthetic method for preparing thiosulfonates on basis of sulfinic acid sodium salt disproportionated reaction
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The invention relates to a synthetic method for preparing thiosulfonates on the basis of a sulfinic acid sodium salt disproportionated reaction. The preparation method comprises the steps that sulfinic acid sodium salts serve as the raw materials, boron trifluoride diethyl etherate serves as accelerant, dichloromethane serves as solvent, and by means of a disproportionation coupled reaction, a thiosulfinate compound with good biological activity is synthesized; two different sulfinic acid sodium salts serve as the raw materials, and by means of a crossed disproportionation coupled reaction method, an asymmetric thiosulfinate compound can be synthesized. By means of a one-pot method and a two-step method, and by means of a thiosulfonates intermediate prepared on site, a sulfones compound and a sulfonamides compound can be synthesized by directly starting from sulfinic acid sodium salts. Accordingly, a synthetic route for preparing thiosulfonates on the basis of the sulfinic acid sodiumsalt disproportionated reaction is provided for the first time, operation is easy, raw materials are easy to obtain, the condition is mild, no metal catalyst is needed, no additional oxidant or reductant is needed, and the prepared thiosulfonates can have the good biological activity, and can also serve as the intermediate of the reaction to be applied to organic synthesis.
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Paragraph 0021; 0022; 0024; 0061-0064
(2018/10/19)
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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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- Convenient and Efficient Diastereoselective Preparation of Functionalized Z-Alkenyl Sulfides
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We have developed an efficient and convenient regio- and stereoselective reduction of the alkynyl sulfides with pinacolborane in the presence of copper(I) chloride to produce (Z)-alkenyl sulfides in good and very good yields. The functionalized alkynyl sulfides are readily available based on the reaction of lithium acetylides with thiotosylates under mild conditions.
- Doroszuk, Justyna,Musiejuk, Mateusz,Ponikiewski, ?ukasz,Witt, Dariusz
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p. 6333 - 6337
(2018/11/01)
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