- Lewis Base/Bronsted Acid Dual-Catalytic C-H Sulfenylation of Aromatics
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A Lewis base/Bronsted acid catalyzed aromatic sulfenylation is reported. These studies demonstrated that the incorporation of electron-rich sulfenyl groups proceeded in the absence of a Lewis base, with kinetic studies indicating an autocatalytic mechanism. The incorporation of electron-poor sulfenyl groups demonstrated little autocatalysis necessitating the use of a Lewis base. This method proved amenable to diverse arenes and heterocycles and was effective in the context of the late-stage functionalization of biologically active small molecules.
- Nalbandian, Christopher J.,Brown, Zachary E.,Alvarez, Erik,Gustafson, Jeffrey L.
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- Sulfone-stabilized carbanions for the reversible covalent capture of a posttranslationally-generated cysteine oxoform found in protein tyrosine phosphatase 1B (PTP1B)
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Redox regulation of protein tyrosine phosphatase 1B (PTP1B) involves oxidative conversion of the active site cysteine thiolate into an electrophilic sulfenyl amide residue. Reduction of the sulfenyl amide by biological thiols regenerates the native cystei
- Parsons, Zachary D.,Ruddraraju, Kasi Viswanatharaju,Santo, Nicholas,Gates, Kent S.
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- Catalytic enantioselective oxysulfenylation ofo-vinylanilides
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Tf2NH-assisted BINAM-derived thiophosphoramide catalysis has been accomplished for the enantioselective oxysulfenylation ofo-vinylanilides withN-(aryl/alkylthio)imides. The developed reaction offers access to diverse substituted aryl/alkylthio
- Anbarasan, Pazhamalai,Kesavan, Arunachalam
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supporting information
p. 282 - 285
(2022/01/06)
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- 3-Thiolated pyrroles/pyrrolines: controllable synthesis and usage for the construction of thiolated fluorophores
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Thiolation/cyclization of homopropargylic tosylamides allowed the selective synthesis of 3-thiolated pyrroles and pyrrolines controlled by solvents. Moreover, the desired 3-thiolated pyrroles were readily transformed to organic fluorophores benzothienopyrrole and bisthiolated boron dipyrromethene (S-BODIPY).
- Tian, Jun,Yuan, Kang-Ning,Liu, Wen,Chang, Hong-Hong,Li, Xing,Gao, Wen-Chao
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supporting information
p. 1943 - 1946
(2021/03/02)
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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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- Regioselective C-H Thioarylation of Electron-Rich Arenes by Iron(III) Triflimide Catalysis
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A mild and regioselective method for the preparation of unsymmetrical biaryl sulfides using iron(III) catalysis is described. Activation of N-(arylthio)succinimides using the powerful Lewis acid iron(III) triflimide allowed the efficient thiolation of a range of arenes, including anisoles, phenols, acetanilides, and N-heterocycles. The method was applicable for the late-stage thiolation of tyrosine and tryptophan derivatives and was used as the key step for the synthesis of pharmaceutically relevant biaryl sulfur-containing compounds such as the antibiotic dapsone and the antidepressant vortioxetine. Kinetic studies revealed that while N-(arylthio)succinimides bearing electron-deficient arenes underwent thioarylation catalyzed entirely by iron(III) triflimide, N-(arylthio)succinimides with electron-rich arenes displayed an autocatalytic mechanism promoted by the Lewis basic product.
- Dodds, Amy C.,Sutherland, Andrew
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p. 5922 - 5932
(2021/05/04)
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- Catalytic Electrophilic Thiocarbocyclization of Allenes
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An efficient approach via catalytic electrophilic thiocarbocyclization of allenes to construct indene-based sulfides with excellent regioselectivities is disclosed. The reactions were carried out at low temperatures by selenide catalysis in the presence o
- Jiang, Quanbin,Li, Huimin,Zhao, Xiaodan
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supporting information
p. 8777 - 8782
(2021/11/17)
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- Enantioselective Construction of Axially Chiral Amino Sulfide Vinyl Arenes by Chiral Sulfide-Catalyzed Electrophilic Carbothiolation of Alkynes
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The enantioselective construction of axially chiral compounds by electrophilic carbothiolation of alkynes is disclosed for the first time. This enantioselective transformation is enabled by the use of a Ts-protected bifunctional sulfide catalyst and Ms-protected ortho-alkynylaryl amines (Ts=tosyl; Ms=mesyl). Both electrophilic arylthiolating and electrophilic trifluoromethylthiolating reagents are suitable for this reaction. The obtained products of axially chiral vinyl–aryl amino sulfides can be easily converted into biaryl amino sulfides, biaryl amino sulfoxides, biaryl amines, vinyl–aryl amines, and other valuable difunctionalized compounds.
- Ji, Jieying,Jiang, Quanbin,Liang, Yaoyu,Luo, Jie,Zhang, Xiaoyan,Zhao, Xiaodan
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supporting information
p. 4959 - 4964
(2020/02/11)
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- In Situ Activation of Disulfides for Multicomponent Reactions with Isocyanides and a Broad Range of Nucleophiles
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Activation of disulfides with N-halogen succinimide in the presence of TEMPO allows insertion reaction by an isocyanide, the product of which can further accept a wide range of nucleophiles for the generation of isothioureas and related molecular moieties. This new procedure overcomes previous methods that accept essentially only aryl amines as the third nucleophilic component. The diverse nucleophiles usable in our new protocol make this approach a general method for de novo synthesis of many S-containing heterocycles.
- Lei, Xiaofang,Wang, Yuanyuan,Fan, Erkang,Sun, Zhihua
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supporting information
p. 1484 - 1487
(2019/02/26)
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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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- h-BN@Copper(II) nanomaterial catalyzed cross-coupling reactions between sulfoximines and N-(phenylthio)-succinimide under mild condition
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A novel and efficient method for the synthesis of N-S substituted sulfoximines has been established with h-BN-supported copper(II) nanomaterial as the catalyst. Catalyzed by this heterogeneous catalyst, the desired products were obtained with wide scope of substrates, good to excellent yields, free ligand and low-toxicity solvent. Moreover, after being reused ten times, there is almost no significant loss of its catalytic activity.
- Lin, Yan,Guanghui,Liu, Yanzhao,Zheng, Yang,Nie, Ruifang,Guo, Li,Wu, Yong
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- iSPAAC: Isomer-Free Generation of a Bcl-xL-Inhibitor in Living Cells
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Strain-promoted azide–alkyne cycloadditions (SPAAC) have proven extremely useful for labeling of biomolecules, but typically produce isomeric mixtures. This is not appropriate for the formation of bioactive molecules in living cells. Here, the first use o
- Lis, Christian,Rubner, Stefan,Gr?st, Corinna,Hoffmann, Ralf,Knappe, Daniel,Berg, Thorsten
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supporting information
p. 13762 - 13766
(2018/09/14)
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- A conjugate Lewis base-Br?nsted acid catalyst for the sulfenylation of nitrogen containing heterocycles under mild conditions
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Catalysts that contain a thiourea tethered to a carboxylic acid were found to affect the sulfenylation of indoles and other N-heterocycles on the hour time scale at room temperature. The mild nature of these conditions allowed for the incorporation of diverse functionalities into more complex heterocycles.
- Nalbandian, Christopher J.,Miller, Eric M.,Toenjes, Sean T.,Gustafson, Jeffery L.
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supporting information
p. 1494 - 1497
(2017/02/05)
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- "On water" catalytic enantioselective sulfenylation of deconjugated butyrolactams
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The first catalytic enantioselective α-sulfenylation of deconjugated butyrolactams has been developed using dimeric cinchona alkaloids as catalysts in a water-enriched reaction medium. Highly substituted and densely functionalized γ-lactams, bearing a qua
- Singha Roy, Soumya Jyoti,Mukherjee, Santanu
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supporting information
p. 6921 - 6925
(2017/09/01)
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- AlCl3-Catalyzed Intermolecular Annulation of Thiol Derivatives and Alkynes by 1,2-Sulfur Migration: Construction of 6-Substituted Benzo[b]thiophenes
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A method for the AlCl3-catalyzed intermolecular oxidative annulation of N-(arylthio)phthalimide derivatives with alkynes has been developed. The annulation reaction occurs at room temperature and involves the oxidative cleavage of the S–N bond and 1,2-sulfur migration, which leads to the construction of diverse arrays of π-conjugated 6-substituted 2,3-diarylbenzo[b]thiophene derivatives.
- Ramesh,Guntreddi, Tirumaleswararao,Sahoo, Akhila K.
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p. 4405 - 4413
(2017/08/23)
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- Synthesis of 3-Sulfenylated Coumarins: BF3·Et2O-Mediated Electrophilic Cyclization of Aryl Alkynoates Using N-Sulfanylsuccinimides
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A simple and efficient metal-free sulfenylation/cyclization of aryl alkynoates has been developed, obtaining various 3-sulfenylated coumarins in moderate to excellent yields. In the presence of BF3·Et2O, the stable and readily access
- Gao, Wen-Chao,Liu, Tao,Zhang, Bing,Li, Xing,Wei, Wen-Long,Liu, Qiang,Tian, Jun,Chang, Hong-Hong
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p. 11297 - 11304
(2016/11/29)
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- Synthesis of Aryl Sulfides: Metal-Free C-H Sulfenylation of Electron-Rich Arenes
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A simple, efficient, and practical metal-free C-H sulfenylation of substituted electron-rich arenes has been developed. This method is highly regioselective, and the corresponding aryl sulfides were obtained in moderate to excellent yields from stable and
- Hostier, Thomas,Ferey, Vincent,Ricci, Gino,Gomez Pardo, Domingo,Cossy, Janine
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supporting information
p. 3898 - 3901
(2015/08/18)
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- TFA-promoted direct C-H sulfenylation at the C2 position of non-protected indoles
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A simple, efficient and practical metal-free C-H sulfenylation process at the C2 position of non-protected indoles has been developed. 2-Thioindoles were obtained in moderate to high yields using stable and readily available N-(thio)succinimides at room temperature in the presence of TFA.
- Hostier, Thomas,Ferey, Vincent,Ricci, Gino,Pardo, Domingo Gomez,Cossy, Janine
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supporting information
p. 13898 - 13901
(2015/09/07)
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- Palladium catalyzed aryl(alkyl)thiolation of unactivated arenes
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A general palladium-catalyzed aryl(alkyl)thiolation of various substituted unactivated arenes is accomplished for the synthesis of diverse unsymmetrical diaryl(alkyl) sulfides in good yield employing electrophilic sulfur reagent 6 derived from succinimide. The developed strategy was coupled with intramolecular arylation of a C-H bond to afford dibenzothiphene derivatives, an important moiety in material science as organic semiconductors.
- Saravanan, Perumal,Anbarasan, Pazhamalai
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supporting information
p. 848 - 851
(2014/03/21)
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- Nucleophilic substitution approach to 4′-substituted thymidines by employing 4′-benzenesulfonyl leaving group
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Synthesis of 4′-substituted thymidines was investigated based on nucleophilic substitution using organosilicon and organoaluminum reagents. Two substrates having a benzenesulfonyl leaving group at the 4′-position were prepared for this purpose: 1-[4-benzenesulfonyl-3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-α-l-threo-pentofuranosyl]thymine (8α) and the 4′-(benzenesulfonyl)thymidine derivative (8β). The reaction of 8α with organosilicon reagents (Me3SiCH2CH{double bond, long}CH2 and Me3SiN3) in combination with SnCl4 gave preferentially the 4′-substituted β-d-isomer: the 4′-allyl (12β) and 4′-azido (15β) derivatives, respectively. The reaction of 8α with AlMe3, however, gave the 4′-methyl-α-l-isomer (16α) as the major product, presumably through an ion pair mechanism. By employing the substrate 8β in this reaction, the 4′-methylthymidine derivative (16β) was obtained exclusively in high yield. The 4′-ethyl (20β) and 4′-cyano (24β) derivatives were also synthesized by reacting 8β with the respective organoaluminum reagent.
- Shimada, Hisashi,Kikuchi, Satoshi,Okuda, Saori,Haraguchi, Kazuhiro,Tanaka, Hiromichi
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experimental part
p. 6008 - 6016
(2011/03/18)
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- Sulfenylation chemistry using polymer-supported sulfides
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Clean sulfenylations are observed upon reaction of activated methylenes with phenyl succinimidyl sulfide. When working with diethyl benzylmalonate, the sulfenylated product can be selectively oxidized and thermally fragmented affording phenylsulfenic acid
- Forbes, David C.,Bettigeri, Sampada V.,Al-Azzeh, Nahla N.,Finnigan, Brian P.,Kundukulam, Joseph A.
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experimental part
p. 1855 - 1857
(2009/07/19)
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- ARYLTHIOINDOLE TUBULIN POLYMERIZATION INHIBITORS AND METHODS OF TREATING OR PREVENTING CANCER USING SAME
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The present invention features arylthioindole compounds, pharmaceutical compositions of arylthioindole compounds and methods of treating a patient suffering from cancer or inflammatory, cardiac, or helminthic diseases, the method comprising administering
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Page/Page column 42
(2010/11/08)
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- Process for the preparation of phosphorothioate triesters
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A process for the synthesis of a phosphorothioate triester is provided. The process comprises the coupling of an H-phosphonate with an alcohol in the presence of a solution comprising both a coupling agent and a sulfur transfer agent. Preferably, the H-ph
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- Inhibitors of HIV reverse transcriptase
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Novel indole compounds inhibit HIV reverse transcriptase, and are useful in the prevention or treatment of infection by HIV and the treatment of AIDS, either as compounds, pharmaceutically acceptable salts, pharmaceutical composition ingredients, whether or not in combination with other antivirals, anti-infectives, immunomodulators, antibiotics or vaccines. Methods of treating AIDS and methods of preventing or treating infection by HIV are also described.
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- Synthesis of α-thiohemiaminal derivatives of deoxynupharidine
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Disulfides, sulfenyl chlorides, thiosulfonates, and sulfensuccinimides were evaluated as electrophilic thiating agents for converting the enamine 6-dehydroxynupharidine to α-thiohemiaminal derivatives of the alkaloid deoxynupharidine.Sulfensuccinimides we
- LaLonde, Robert T.,Eckert, Timothy S.
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p. 2298 - 2302
(2007/10/02)
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