5219-61-4Relevant articles and documents
Transition-metal-free decarboxylative thiolation of stable aliphatic carboxylates
Xing, Wei-Long,Liu, De-Guang,Fu, Ming-Chen
, p. 4593 - 4597 (2021/02/03)
A transition-metal-free decarboxylative thiolation protocol is reported in which primary, secondary, tertiary (hetero)aryl acetates and α-CN substituted acetates undergo the decarboxylative thiolation smoothly, to deliver a variety of functionalized aryl alkyl sulfides in moderate to excellent yields. Aryl diselenides are also amenable substrates for construction of C-Se bonds under the simple and mild reaction conditions. Moreover, the protocol is successfully applied to the late-stage modification of pharmaceutical carboxylates with satisfactory chemoselectivity and functional-group compatibility. This journal is
Rhodium-catalyzed Sommelet-Hauser type rearrangement of α-diazoimines: Synthesis of functionalized enamides
Anbarasan, Pazhamalai,Ramachandran, Kuppan,Reddy, Angula Chandra Shekar,Reddy, Palagulla Maheswar
supporting information, p. 5649 - 5652 (2020/06/09)
An efficient rhodium catalyzed Sommelet-Hauser type rearrangement of sulfur ylides derived from α-thioesters and N-sulfonyl-1,2,3-triazoles has been successfully accomplished for the synthesis of various functionalized enamides. The developed reaction involves the unprecedented [2,3]-sigmatropic rearrangement of sulfur ylides with the imine motif. Importantly, the method works well with various substituted α-thioesters/-amides/-ketones and substituted N-sulfonyl-1,2,3-triazoles and allows the synthesis of diverse enamide derivatives in good to excellent yields. The reaction was also successfully extended to the one-pot synthesis of enamides from terminal alkynes.
Sulfoxide Reduction/C(sp3)-S Metathesis Cascade in Ionic Liquid
Liu, Chenjing,Chen, Dengfeng,Fu, Yuanyuan,Wang, Fei,Luo, Jinyue,Huang, Shenlin
supporting information, p. 5701 - 5705 (2020/07/24)
A sulfoxide reduction/C-S bond metathesis cascade between sulfoxides and alkyl bromides has been developed to access high-value sulfides without the use of any catalysts or bases. In this cascade, classical Kornblum oxidation is employed to reduce sulfoxides with alkyl bromides in ionic liquid. This protocol features high functional tolerance, mild conditions, promising scalability, and sustainable solvents.
Compound, preparation method thereof, medical intermediate and application thereof
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Paragraph 0060-0067, (2020/08/06)
The invention relates to the technical field of chemical synthesis, and particularly discloses a compound, a preparation method thereof, a medical intermediate and an application thereof, the compoundcomprises the following raw materials: thioether, bromide and a proper amount of organic solvent, and the molar weight ratio of thioether to bromide is 1: (2-8). According to the compound provided bythe invention, thioether, bromide and a proper amount of organic solvent are used as raw materials, and the thioether compound can be obtained without adopting a catalyst, so that the problems of metal residues and the like are fundamentally eliminated, the provided preparation method is simple to operate, the method is simple in process and high in yield, the thioether compound is prepared through thioether metathesis reaction, metal catalysis is not needed in the whole reaction, meanwhile, the reaction condition is mild, the substrate range is wide, the problem of metal pollution existing in an existing thioether compound synthesis method is solved, and the method has wide market prospects in the fields of organic synthesis, medicine synthesis and the like.
Rhodium-Catalyzed Rearrangement of S/Se-Ylides for the Synthesis of Substituted Vinylogous Carbonates
Reddy, Angula Chandra Shekar,Anbarasan, Pazhamalai
supporting information, p. 9965 - 9969 (2019/12/24)
An efficient rhodium-catalyzed unprecedented oxa-[2,3]-sigmatropic rearrangement of sulfur ylide derived from α-thioesters/ketones and diazo carbonyl compounds has been accomplished for the synthesis of various sulfur-tethered vinylogous carbonates in good to excellent yields. Important features of the developed reaction include wide functional group tolerance, excellent chemo- and regioselectivity, and efficient rearrangement involving the carbonyl motif. The present reaction also equally works well with α-selenoesters for the synthesis of seleno-containing vinylogous carbonates.
Dealkylative intercepted rearrangement reactions of sulfur ylides
Empel, Claire,Hock, Katharina J.,Koenigs, Rene M.
supporting information, p. 338 - 341 (2019/01/09)
Sulfur ylides are well-known to undergo sigmatropic rearrangement reaction. Herein, we describe a novel reactivity of sulfur ylides, which provides access to the product of a formal functional group metathesis upon dealkylative interception of the rearrangement process. Using a simple iron catalyst and in situ generated diazoalkanes this method provides access to α-mercaptoacetonitrile derivatives.
Iron-catalysed carbene-transfer reactions of diazo acetonitrile
Empel, Claire,Hock, Katharina J.,Koenigs, Rene M.
supporting information, p. 7129 - 7133 (2018/10/24)
A continuous-flow protocol for the synthesis of diazo acetonitrile was developed. It was further applied in iron-catalysed insertion reactions of diazo acetonitrile into N-H and S-H bonds to yield valuable α-substituted acetonitrile, including gram-scale synthesis.
Aryl sulfoxide, thioether compound, synthesis method and application thereof
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Paragraph 0197-0200, (2018/04/21)
The invention discloses a method for selective synthesis of an aryl sulfoxide compound (III) and an aryl thioether compound (IV). According to the invention, in a reactive solvent, an aryl high iodinesalt is adopted as the reaction raw material, aryl/alkyl thiosulfate is taken as the vulcanizing reagent, under the catalysis of visible light and a photosensitive reagent, and under the action of lewis acid and alkali, when the reaction atmosphere is nitrogen, the thioether compound (IV) can be generated, and when the reaction atmosphere is air, the sulfoxide compound (III) can be generated. Thesynthesis method provided by the invention has the advantages of easily available and cheap raw materials, simple reaction operation, mild and environment-friendly reaction conditions, high yield, and excellent functional group tolerance. The invention also discloses the new aryl sulfoxide compound (III) and aryl thioether compound (IV), also successfully realizes later modification of drugs andsugar, and realizes the formal synthesis of some drugs, and provides an efficient method for selective construction of thioether and sulfoxide compounds.
Inhibitors of the Diadenosine Tetraphosphate Phosphorylase Rv2613c of Mycobacterium tuberculosis
G?tz, Kathrin H.,Hacker, Stephan M.,Mayer, Daniel,Dürig, Jan-Niklas,Stenger, Steffen,Marx, Andreas
, p. 2682 - 2689 (2017/10/27)
The intracellular concentration of diadenosine tetraphospate (Ap4A) increases upon exposure to stress conditions. Despite being discovered over 50 years ago, the cellular functions of Ap4A are still enigmatic. If and how the varied Ap4A is a signal and involved in the signaling pathways leading to an appropriate cellular response remain to be discovered. Because the turnover of Ap4A by Ap4A cleaving enzymes is rapid, small molecule inhibitors for these enzymes would provide tools for the more detailed study of the role of Ap4A. Here, we describe the development of a high-throughput screening assay based on a fluorogenic Ap4A substrate for the identification and optimization of small molecule inhibitors for Ap4A cleaving enzymes. As proof-of-concept we screened a library of over 42, 000 compounds toward their inhibitory activity against the Ap4A phosphorylase (Rv2613c) of Mycobacterium tuberculosis (Mtb). A sulfanylacrylonitril derivative with an IC50 of 260 ± 50 nM in vitro was identified. Multiple derivatives were synthesized to further optimize their properties with respect to their in vitro IC50 values and their cytotoxicity against human cells (HeLa). In addition, we selected two hits to study their antimycobacterial activity against virulent Mtb to show that they might be candidates for further development of antimycobacterial agents against multidrug-resistant Mtb.
Controllable Sulfoxidation and Sulfenylation with Organic Thiosulfate Salts via Dual Electron- and Energy-Transfer Photocatalysis
Li, Yiming,Wang, Ming,Jiang, Xuefeng
, p. 7587 - 7592 (2017/11/10)
Sulfoxides and sulfides are two important functional groups in organic molecules, containing different valence states of sulfur. Both sulfoxidation and sulfenylation with common sulfurating reagents were successfully tuned via a facile variation of the atmosphere under photocatalyzed conditions. The sulfoxidation and sulfenylation transformations involved tandem electron-/energy-transfer and single-electron-transfer processes, respectively. Late-stage sulfoxidation for pharmaceuticals and sugar derivatives was established to be highly compatible. Divergent formal syntheses of sulfoxide/sulfide-containing marketed pharmaceuticals were switchably implemented. Gram-scale operations further demonstrated the practicability of the protocol.
