1153-43-1Relevant articles and documents
Synthesis of Symmetrical and Unsymmetrical Thiosulfonates from Disulfides through Electrochemically Induced Disulfide Bond Metathesis and Site-Selective Oxidation
Strehl, Julia,Hilt, Gerhard
supporting information, (2021/10/14)
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.
Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
, p. 9291 - 9298 (2021/11/13)
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
H4SiW12O40-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides: An efficient synthesis of 3,4-disubstituted 1H-pyrazoles
Cheng, Mengyuan,Cheng, Yuanyuan,Gao, Xiaofei,Li, Ke,Lin, Xiaoling,Liu, Yufeng,Xie, Xuanjie,Yang, Guoping
supporting information, (2021/09/06)
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.
Synthesis of symmetrical / unsymmetrical thiosulfonates through the disproportionate coupling reaction of sulfonyl hydrazide mediated by phosphomolybdic acid
Lv, Mengting,Liu, Yufeng,Li, Ke,Yang, Guoping
supporting information, (2021/01/21)
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.
Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides
Zhang, Guofu,Fan, Qiankun,Zhao, Yiyong,Wang, Huimin,Ding, Chengrong
supporting information, p. 81 - 85 (2020/11/03)
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.
Metal-Free Radical Annulation of Oxygen-Containing 1,7-Enynes: Configuration-Selective Synthesis of (E)-3-((Arylsulfonyl)methyl)-4-Substituted Arylidenechromene Derivatives
Bian, Mouwang,Dai, Lei,Mao, Kaimin,Rong, Liangce,Wang, Chang,Yu, Qiuyu,Zhang, Jinghang
supporting information, p. 218 - 224 (2021/01/13)
A novel strategy for the synthesis of (E)-3-((arylsulfonyl)methyl)-4-substituted benzylidenechromene derivatives via a metal-free radical annulation reaction of oxygen-containing 1,7-enynes with thiosulfonates has been developed. The reaction shows broad substrate scope, wide functional group tolerance, and moderate to excellent yields. Moreover, thiosulfonates were well driven to achieve the bifunctionalization reaction of oxo-1,7-enynes which derived from aliphatic alkynes. In addition, the (E)-configuration of the products was highly controlled by the structure of 1,7-enyne.
S-(4-Methoxyphenyl)-4-methoxybenzenesulfonothioate as a Promising Lead Compound for the Development of a Renal Carcinoma Agent
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
, p. 449 - 458 (2020/01/25)
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.
Electrochemical synthesis of sulfinic esters from alcohols and thiophenols
He, Yang,Zhang, Jinli,Xu, Liang,Wei, Yu
supporting information, (2020/01/31)
Electrochemical oxidative couplings between S[sbnd]H and O[sbnd]H bonds are achieved herein directly from readily-available alcohols and thiophenols, affording a series of diverse sulfinic esters. This strategy can take advantage of 6 equivalents of alcohol, relative to thiophenol, to achieve moderate to good yields, without the assistance of any metallic catalysts, bases, and additional oxidants.
CuCl2-promoted decomposition of sulfonyl hydrazides for the synthesis of thiosulfonates
Kim, Junsu,Park, Sanggil,Kim, Hyungjun,Kim, Jinho
supporting information, (2020/07/02)
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.
Electrochemical oxidations of thioethers: Modulation of oxidation potential using a hydrogen bonding network
Liu, Shiwen,Chen, Bocheng,Yang, Yi,Yang, Yuhao,Chen, Qianjin,Zeng, Xiaojun,Xu, Bo
, (2019/11/28)
A highly efficient chemo-selective electrochemical oxidation of thioethers to sulfoxides and sulfones was developed. The hydrogen bonding network generated from hexafluoro-2-propanol (HFIP) and acetic acid (AcOH) plays an important role in the modulation of oxidation potential. The hydrogen bonding network complexes strongly with the sulfoxide, making it less prone to further oxidation. Therefore, thioethers can be selectively electrochemically oxidized to sulfoxides and over-oxidization could be minimized. Moreover, this modulation of oxidization via hydrogen bonding was supported by density functional theory (DFT) calculations and cyclic voltammetry experiments.
