- Cycloaddition Reactions of Highly Stabilized Isoquinolinium Methylides to Nonactivated Olefins and Electron-Rich Olefins
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Highly stabilized isoquinolinium methylides bearing two electron-withdrawing substituents at the ylide carbon undergo cycloadditions with aryl-substituted olefins (acenaphthylene,(E)- and (Z)-stilbenes, indene, and stirene), alkyl-substituted olefins (norbornene, (Z)-3-hexene-1,6-dinitrile, 1-hexene, 2-propen-1-ol, and 3-(trimethylsilyloxy)propene), and electron-rich olefins (vinylene carbonate, butyl vinyl ether, and phenyl vinyl sulfide).These cycloadditions proceed in an exclusively regioselective and mostly stereoselective manner.
- Tsuge, Otohiko,Kanemasa, Shuji,Sakamoto, Kazushige,Takenaka, Shigeori
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- Reactions of arenediazonium salts with diazadithiafulvalenes
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The kinetics of coupling of carbon radicals with sulfur radical-cations in diazadithiafulvalenes is sensitive to the steric environment around sulfur.
- Koizumi, Toshio,Bashir, Nadeem,Murphy, John A.
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- Structure-activity relationships of phenyl- and benzoylpyrroles
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Antitumor, antimicrobial, and phytotoxic activities of the marine antibiotic pentabromopseudilin (la) and related phenyl-, benzyl- and benzoyl pyrroles were compared. All activities depended strongly on the substituent pattern, with the natural compound 1a being the most active one. As judged from model reactions, a covalent bond of nucleophiles to the pyrrole system may be involved in the inhibition of macromolecular syntheses.
- Laatsch,Renneberg,Hanefeld,Kellner,Pudleiner,Hamprecht,Kraemer,Anke
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- Electrogeneration of triphenyltin radical, anion, and cation. Electrochemical initiation of tin hydride-promoted radical chain reactions
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In our research of precursors of tin radicals able to initiate radical chain reactions under mild conditions, a series of triphenyltin derivatives Ph3SnY (Y = H, I, Cl, OTf, OCHO, SnPh3, SPh) is investigated by cyclic voltammetry. The results show that the tin radical Ph3Sn. is only produced from two compounds: by a one-electron oxidation of Ph3SnH or by a one-electron reduction of Ph3-SnI. Therefore electrooxidation of Ph3SnH generates Ph3Sn. which is able to initiate cyclization of haloalkynes. Reduction or oxidation of the other derivatives affords respectively the anion Ph3Sn- or the cation Ph3Sn+ because they are generated at potentials where the radical Ph3Sn. is either reduced or oxidized.
- Tanaka, Hideo,Ogawa, Hidenori,Suga, Hiroaki,Torii, Sigeru,Jutand, Anny,Aziz, Said,Suarez, Alejandra G.,Amatore, Christian
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- Metal- and solvent-free, iodine-catalyzed cyclocondensation and C[sbnd]H bond sulphenylation: A facile access to C-4 sulfenylated pyrazoles via a domino multicomponent reaction
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We describe herein a green and efficient MCRs protocol to synthesize C-4 sulfenylated pyrazoles by iodine-catalyzed cyclocondensation and direct C[sbnd]H bond sulphenylation reactions. Through this protocol, two new C[sbnd]N bonds and one C[sbnd]S bond ar
- Sun, Pengfei,Yang, Daoshan,Wei, Wei,Sun, Xuejun,Zhang, Wenhui,Zhang, Hui,Wang, Yu,Wang, Hua
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- Visible-light-mediated defluorinative cross-coupling of: Gem-difluoroalkenes with thiols
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Here we report a visible-light-mediated monofluoroalkenylation through defluorinative cross-coupling of gem-difluoroalkenes with aryl, benzyl, and alkyl thiols. This novel strategy provides facile and efficient access to tri/tetra-substituted monofluoroalkenes under mild reaction conditions with good functional group tolerance. Late-stage modification of natural products indicated the synthetic potential of this S-H monofluoroalkenylation process.
- Wang, Junlei,Huang, Binbin,Yang, Chao,Xia, Wujiong
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- Stereoselective access to trisubstituted fluorinated alkenyl thioethers
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We report the first copper-catalyzed olefinic ethoxy carbonyl difluoromethylation of alkenyl thioethers via direct C-H bond functionalization using BrCF2COOEt. The developed methodology allows the preparation of trisubstituted olefins with a controlled stereochemistry. A mechanistic study is reported and a radical mechanism is revealed.
- Fabre, Indira,Poisson, Thomas,Pannecoucke, Xavier,Gillaizeau, Isabelle,Ciofini, Ilaria,Grimaud, Laurence
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- Rhodium-Catalyzed Asymmetric Ring Opening of Oxabicyclic Alkenes with Sulfur Nucleophiles
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The synthesis of 2-sulfanyl-1,2-dihydro-naphthalen-1-ols is described. This methodology is based on rhodium catalysis and enables various thiols to undergo an asymmetric SN2′ ring opening of oxabenzonorbornadiene. Under the reaction conditions
- Leong, Paul,Lautens, Mark
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- Mixed-chalcogenide diplatinum complexes; an investigation of ligand exchange processes using ESI mass spectrometry
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Routes to mixed-chalcogen diplatinum complexes have been explored using Electrospray Ionisation Mass Spectrometry (ESI-MS) as a powerful technique to probe reaction solutions on the microscale. Exchange reactions of binuclear platinum(II) complexes [Ptsu
- Fortney-Zirker, Ryland G.,Henderson, William,Tiekink, Edward R.T.
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- Cryoelectrochemical reduction of a phenyl sulfide in tetrahydrofuran: Mediated reduction gives different products compared to direct reduction
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An electrocatalytic reduction of [(3-{[trans-4-(methoxymethoxy)cyclohexyl] oxy}propyl)thio]benzene (RSPh) in the presence of naphthalene as a mediator is investigated, using steady-state voltammetry at various sized platinum microelectrodes and at low temperature (201 K) in tetrahydrofuran (THF). This mediated process has been found to involve the transfer of one electron, in contrast to the direct electrochemical reduction which involves two electrons. In addition, the mediated reduction proceeds at a potential, some 500mV less negative than the direct electrochemical reduction. The evidence for the proposed mechanism has been obtained from theoretical simulations, using DIGISIM which shows satisfactory fitting to experimental results and allowed the determination of the rate constant for the homogeneous step. In contrast to direct reduction of RSPh where only one product, trans-1-(methoxymethoxy)-4- propoxycyclohexane (RH), has been obtained, the isolation of two products, RH and the dimer, diphenyl disulfide, PhSSPh, following mediated preparative electrolysis of RSPh, in presence of naphthalene shows that this one-electron process may be carried out at the reduction potential of naphthalene at low temperature and has also validated deductions made from voltammetric results. Copyright
- Burasov, Alexander V.,Paddon, Christopher A.,Bhatti, Earrah L.,Donohoe, Timothy J.,Compton, Richard G.
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- The phenyl thiyl radical as initiator in vinyl polymerizations. Investigations into the initiation step by the aminoxyl trapping technique
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The reactions of phenyl thiyl radicals with styrene, methyl methacrylate, methacrylonitrile, and vinylacetate in the presence of an aminoxyl radical scavenger have been studied. Two main products were formed: diphenyl disulfide, and the expected product formed by addition of the thiyl radical to the double bond of the monomer followed by trapping by the aminoxyl radical. The relative reactivity of the monomers towards addition of phenyl thiyl radicals at 60°C was: VA:MAN:MMA:STY = 1:50:100:500.
- Busfield, W. Ken,Heiland, Kirstin,Jenkins, Ian D.
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- UV-vis and IR spectroscopic characterization of diphenyl disulfide radical cation in acid zeolites and its rearrangement to thianthrenium radical cation
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Adsorption of diphenyl disulfide (DPDS) from CH2Cl2 solutions onto acid zeolites at room temperature generated the "extended" radical cation, DPDS.+. At loadings of 3 wt%, oxidation to DPDS.+ is essentially complete. Upon heating the loaded zeolite to 200°C, the adsorbed DPDS.+ was converted into thianthrenium radical cation (TH.+). Ab initio calculations at the B3LYP and HF levels using the 6-31G* basis set suggest cyclization of a diphenyl disulfide-S,S-dication as a reasonable rate-determining step of the conversion. Non-acidic zeolites devoid of Lewis and Bronsted sites (as determined by the pyridine adsorption-desorption method) failed to generate DPDS.+ to an extent detectable spectroscopically: these results support Lewis and/or Bronsted sites as being responsible for the observed oxidation.
- Marti, Vicente,Fernandez, Lorenzo,Fornes, Vicente,Garcia, Hermenegildo,Roth, Heinz D.
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- Tetrathiatetraza-azulene; Synthesis and X-Ray Crystal Structure
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Tetrasulphur tetranitride and phenyl vinyl sulphoxide or sulphone react to give a novel planar delocalised 14? electron aromatic system, 1λ4δ2,3,5,7λ4δ2-tetrathia-2,4,6,8-tetraza-azulene (4) in which all the S4N4 atoms have been retained; the molecules from parallel overlapping stacks with a minimum interplanar atomic separation of 3.26 Angstroem.
- Jones, Ray,Morris, Janet L.,Rees, Charles W.,Williams, David J.
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- Chromoselective Synthesis of Sulfonyl Chlorides and Sulfonamides with Potassium Poly(heptazine imide) Photocatalyst
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Among external stimuli used to promote a chemical reaction, photocatalysis possesses a unique one—light. Photons are traceless reagents that provide an exclusive opportunity to alter chemoselectivity of the photocatalytic reaction varying the color of incident light. This strategy may be implemented by using a sensitizer capable to activate a specific reaction pathway depending on the excitation light. Herein, we use potassium poly(heptazine imide) (K-PHI), a type of carbon nitride, to generate selectively three different products from S-arylthioacetates simply varying the excitation light and otherwise identical conditions. Namely, arylchlorides are produced under UV/purple, sulfonyl chlorides with blue/white, and diaryldisulfides at green to red light. A combination of the negatively charged polyanion, highly positive potential of the valence band, presence of intraband states, ability to sensitize singlet oxygen, and multi-electron transfer is shown to enable this chromoselective conversion of thioacetates.
- Antonietti, Markus,Guldi, Dirk M.,Markushyna, Yevheniia,Savateev, Aleksandr,Schü?lbauer, Christoph M.,Ullrich, Tobias
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supporting information
p. 20543 - 20550
(2021/08/12)
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- One-Pot Synthesis of N-Iodo Sulfoximines from Sulfides
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This is the first report on the synthesis and characterization of N-iodo sulfoximines. The synthesis was designed as a room temperature one-pot cascade reaction from readily available sulfides as starting compounds, converted into sulfoximines by reaction with ammonium carbonate and (diacetoxyiodo)benzene, followed by iodination with N-iodosuccinimide or iodine in situ, in up to 90% isolated yields, also at a multigram scale. Iodination of aryls with N-iodo sulfoximines, oxidation, and conversion to N-SCF3 congeners have been demonstrated.
- Zupanc, An?e,Jereb, Marjan
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p. 5991 - 6000
(2021/05/05)
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- Synthesis of (E)-iodo vinylsulfones via oxidative addition of thiol into alkyne under metal free condition
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An efficient, transition-metal free and molecular iodine promoted protocol for the construction of (E)-β-iodovinyl sulfone derivatives via oxidative C–S coupling of thiol and alkyne has been demonstrated. Both aryl and alkyl terminal acetylenes were found to be an excellent substrate for the present reaction which provides a wide range of β-iodovinyl sulfone derivatives with very good yield and excellent regio and stereo-selectivities. Diaryldisulfide is also found to be an equally efficient sulfonyl group surrogate under identical reaction conditions.
- Samanta, Surya Kanta,Sarkar, Rumpa,Bera, Mrinal K.
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supporting information
(2021/07/12)
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- Transformation of arylboronic acids with sodium thiosulfate into organodisulfides catalyzed by a recyclable polyoxometalate-based Cr(iii) catalyst
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Organo disulfides represent an abundant class of compounds in chemical biology, pharmaceutical fields, and industry. They are traditionally synthesized by the oxidation of mercaptan in the presence of an organic ligand supported metal catalyst or toxic oxidants under harsh conditions. Here, we disclose a highly-efficient pathway in which disulfide is synthesized by organic boric acid and Na2S2O3 using the catalyst (NH4)3[CrMo6O18(OH)6], demonstrating a high activity and excellent selectivity. Various boric acid derivatives have been successfully transformed into the corresponding disulfides. Mechanistic insights have been furnished based on the observation of intermediate and control experiments.
- Chang, Yalin,Li, Huiyi,Tao, Chaofu,Wang, Aiping,Wei, Yongge,Xie, Ya,Yu, Han,Yu, Shunming
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supporting information
p. 6059 - 6064
(2021/08/23)
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- Direct synthesis of sulfinic esters via ultrasound accelerated tandem reaction of thiols and alcohols with N-bromosuccinimide
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The direct transformation of various thiols and simple alcohols with N-bromosuccinimide into sulfinic esters has been investigated by using different categories of base/acidic catalysts as well as co-solvents under varied reaction conditions. The reaction was found out to afford the sulfinic esters with high yields in the absence of catalysts, especially within the shorter time under the acceleration of ultrasonic irradiation than under the longer-lasting conventional stirring conditions.
- Nguyen, Lan-Anh Thi,Le, Tri-Nghia,Duong, Cong-Thang,Vo, Chi-Tam,Duus, Fritz,Luu, Thi Xuan Thi
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p. 519 - 528
(2021/05/27)
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- NIS-promoted three-component reaction of 3-oxo-3-arylpropanenitriles with arylsulfonyl hydrazides
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A new three-component reaction of 3-oxo-3-arylpropanenitriles with arylsulfonyl hydrazides has been established, and an expanded inventory of 3-aryl-4-(arylthio)-1H-pyrazol-5-amines is synthesized by sequential cyclization and sulfenylation reactions under the action of NIS. In addition to the attractive features of multicomponent reactions, the protocol presents broad substrate scope, good functional group tolerance and mild reaction conditions. The utility of this procedure is further established by gram-scale synthesis as well as the diversified transformations of the products to useful compounds. This journal is
- Wei, Yueting,Liu, Ping,Liu, Yali,He, Jing,Li, Xuezhen,Li, Shiwu,Zhao, Jixing
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p. 3932 - 3939
(2021/05/14)
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- Synthesis, Crystal Structure and Docking Studies as Potential Anti-Inflammatory Agents of Novel Antipyrine Sulfanyl Derivatives
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The InCl3-catalyzed green synthesis of sulfanyl- and oxasulfanyl-substituted antipyrine derivatives (10 examples) through the thiomethylation of the substrate at the С(4)-Н position by formaldehyde and thiols or α,ω-mercaptoalkanols in water has been first developed. An X-ray diffraction study of the structures and molecular packing of compounds 4a, 4c-e demonstrated that the extension of the substitution chain with one methylene unit for compound 4d versus compounds 4а, 4c, and 4e results in the formation of a 2D (network) instead of 1D motif (chains). Using the molecular docking method, objective assumptions were made about the selectivity of anti-inflammatory action for S- and O,S-derivatives of antipyrine.
- Akhmadiev, Nail S.,Akhmetova, Vnira R.,Ibragimov, Askhat G.,Khairullina, Veronica R.,Khalilov, Leonard M.,Mescheryakova, Ekaterina S.
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- Multifunctional core-shell Pd@Cu on MoS2 as a visible light-harvesting photocatalyst for synthesis of disulfide by S[sbnd]S coupling
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Visible light harvesting materials are considered promising cost-effective heterogenous catalysts for organic synthesis. A novel and efficient synthesis of multifunctional core-shell Pd@Cu/MoS2 nanostructures is utilized for synthesis of disulfides by S[sbnd]S Coupling. The Pd@Cu core-shell was obtained by one-pot hydrothermal synthesis, and a simple method was used to load it onto the MoS2. The as-prepared materials were characterized by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, X-ray photoelectron spectroscopy, UV–vis diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The Pd@Cu/MoS2 nanostructures revealed excellent photocatalytic activity, reusability, and stability towards the oxidative coupling of mercaptans to disulfanes. The outstanding photocatalytic activity of Pd@Cu/MoS2 will enhance interest in the field of multifunctional core-shell nanomaterials as photocatalysts for a wide variety of applications.
- Yusuf, Mohammad,Song, Sehwan,Park, Sungkyun,Park, Kang Hyun
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- Generation of H2S from Thiol-Dependent NO Reactivity of Model [4Fe-4S] Cluster and Roussin's Black Anion
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Iron-sulfur clusters (Fe-S) have been well established as a target for nitric oxide (NO) in biological systems. Complementary to protein-bound studies, synthetic models have provided a platform to study what iron nitrosylated products and byproducts are produced depending on a controlled reaction environment. We have previously shown a model [2Fe-2S] system that produced a dinitrosyl iron complex (DNIC) upon nitrosylation along with hydrogen sulfide (H2S), another important gasotransmitter, in the presence of thiol, and hypothesized a similar reactivity pattern with [4Fe-4S] clusters which have largely produced inconsistent reaction products across biological and synthetic systems. Roussin's black anion (RBA), [Fe4(μ3-S)3(NO)7]-, is a previously established reaction product from synthetic [4Fe-4S] clusters with NO. Here, we present a new reactivity for the nitrosylation of a synthetic [4Fe-4S] cluster in the presence of thiol and thiolate. [Et4N]2[Fe4S4(SPh)4] (1) was nitrosylated in the presence of excess PhSH to generate H2S and an "RBA-like"intermediate that when further reacted with [NEt4][SPh] produced a {Fe(NO)2}9 DNIC, [Et4N][Fe(NO)2(SPh)2] (2). This "RBA-like"intermediate proved difficult to isolate but shares striking similarities to RBA in the presence of thiol based on IR υ(NO) stretching frequencies. Surprisingly, the same reaction products were produced when the reaction started with RBA and thiol. Similar to 1/NO, RBA in the presence of thiol and thiolate generates stoichiometric amounts of DNIC while releasing its bridging sulfides as H2S. These results suggest not only that RBA may not be the final product of [4Fe-4S] + NO but also that RBA has unprecedented reactivity with thiols and thiolates which may explain current challenges around identifying biological nitrosylated Fe-S clusters.
- Oakley, Kady M.,Zhao, Ziyi,Lehane, Ryan L.,Ma, Ji,Kim, Eunsuk
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p. 15910 - 15917
(2021/07/20)
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- Electroreductive Nickel-Catalyzed Thiolation: Efficient Cross-Electrophile Coupling for C?S Formation
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Sulfur-containing molecules are of utmost topical importance towards the effective development of pharmaceuticals and functional materials. Herein, we present an efficient and mild electrochemical thiolation by cross-electrophile coupling of alkyl bromide
- Ang, Nate W. J.,Ackermann, Lutz
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supporting information
p. 4883 - 4887
(2021/02/26)
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- Visible-light-promotedE-selective synthesis of α-fluoro-β-arylalkenyl sulfidesviathe deoxygenation/isomerization process
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Regioselective synthesis of α-fluoro-β-arylalkenyl sulfides has been established withgem-difluoroalkenes and sodium sulfinates in a transition-metal-free manner. A series of control experiments were executed to demonstrate thiol radicals and anions as the proposed intermediates. Notably, regioselectiveZ→Eisomerization was achieved under green light irradiation in the absence of a photoinitiator.
- Li, Yuxiu,Li, Xiangqian,Li, Xiaowei,Shi, Dayong
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supporting information
p. 2152 - 2155
(2021/03/06)
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- Substituted o-Aminophenols as Redox-Mediators in the Thiol Oxidation to Unsymmetrical Disulfides
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A number of substituted o-aminophenols has been investigated as redox mediators of the thiol oxidation to disulfides. The electrooxidation of o-aminophenols leads to the corresponding o-iminobenzoquinones. These compounds react with thiols in the solution with a formation of disulfides. It was established that the use of 4,6-di-tert-butyl-2-(tert-butylamino)phenol as a redox mediator can reduce the overpotential of the thiol oxidation by 0.2-1.4 V depending on the nature of the coupling thiols. The unsymmetrical disulfides with alkyl, aryl, and heteroaryl substituents were obtained as the result of the indirect electrosynthesis.
- Berberova, Nadezhda T.,Burmistrova, Daria A.,Galustyan, Andrey,Smolyaninov, Ivan V.
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- Chan-Lam-Type C-S Coupling Reaction by Sodium Aryl Sulfinates and Organoboron Compounds
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A Chan-Lam-Type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in up to 92% yields in the presence of a copper catalyst and potassium sulfite. Both electron-rich and electron-poor sodium aryl sulfinates and diverse organoboron compounds were tolerated for the synthesis of aryl and heteroaryl thioethers and dithioethers. The mechanistic study suggested that potassium sulfite was involved in the deoxygenation of sulfinate through a radical process.
- Lam, Long Yin,Ma, Cong
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supporting information
p. 6164 - 6168
(2021/08/16)
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- Click Reaction of Selenols with Isocyanates: Rapid Access to Selenocarbamates as Peroxide-Switchable Reservoir of Thiol-Peroxidase-Like Catalysts
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Selenols react with isocyanates under mild catalyst-free conditions to generate selenocarbamates in good yield and with high selectivity over potentially competing nucleophilic additions. The methodology enables the incorporation of a wide variety of functional groups providing access to a broad array of densely functionalised selenocarbamates. In the presence of competing heteroatom-centered nucleophiles, isocyanates selectively couple with selenols. Selenocarbamates exhibited thiol-peroxidase-like properties, enabling the reduction of hydrogen peroxide at the expense of thiols, which are converted into the corresponding disulfides. A series of control experiments suggested that the catalytic mechanism proceeds through a pathway, involving a H2O2-promoted transcarbamoylation reaction leading to a thiocarbamate with concomitant releasing of catalytically active selenolate anions. By undergoing peroxide-driven thiol-selenol exchange, selenocarbamates behave as equivalents of selenolate anions with thiol-peroxidase-like activity. (Figure presented.).
- Capperucci, Antonella,Petrucci, Alessandra,Faggi, Cristina,Tanini, Damiano
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supporting information
p. 4256 - 4263
(2021/07/17)
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- Synthesis and application of Cu(II) immobilized MCM-41 based solid Lewis acid catalyst for aminolysis reaction under solvent-free condition
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In this paper, a Cu(II) immobilized periodic mesoporous organosilica (PMOs) was synthesized and used as a reusable solid Lewis acid catalyst for the aminolysis of epoxides under solvent-free conditions. An amide-based ligand, L-propylsilyl (1) having a specific binding pocket was prepared and fabricated on mesoporous MCM-41 to produce mesoporous organosilica L-propylsilyl@MCM-41 (2). Further, it has been utilized for anchoring Cu(II) ions under controlled reaction conditions to yield solid Lewis acid catalyst Cu(II)-L-propylsilyl@MCM-41 (3). The synthesized catalyst 3 exhibits significantly higher catalytic activity for aminolysis compared to hitherto known solid Lewis acid catalysts. An extensive range of β-amino alcohols with high regio and stereoselectivity were prepared by using catalyst 3. The catalyst was recovered easily and reused eight times without any loss in its catalytic activity. Furthermore, the synthesis of clinically significant propranolol (β-blocker) from α- naphthyl glycidyl ether was attained successfully using catalyst 3 in a very decent yield.
- Chaudhary, Garima,Gupta, Neha,Singh, Amit Pratap
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supporting information
(2021/07/22)
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- Metal-free Transformations of Nitrogen-Oxyanions to Ammonia via Oxoammonium Salt
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Transformations of nitrogen-oxyanions (NOx?) to ammonia impart pivotal roles in sustainable biogeochemical processes. While metal-mediated reductions of NOx? are relatively well known, this report illustrates proton-assisted transformations of NOx? anions in the presence of electron-rich aromatics such as 1,3,5-trimethoxybenzene (TMB?H, 1 a) leading to the formation of diaryl oxoammonium salt [(TMB)2N+=O][NO3?] (2 a) via the intermediacy of nitrosonium cation (NO+). Detailed characterizations including UV/Vis, multinuclear NMR, FT-IR, HRMS, X-ray analyses on a set of closely related metastable diaryl oxoammonium [Ar2N+=O] species disclose unambiguous structural and spectroscopic signatures. Oxoammonium salt 2 a exhibits 2 e? oxidative reactivity in the presence of oxidizable substrates such as benzylamine, thiol, and ferrocene. Intriguingly, reaction of 2 a with water affords ammonia. Perhaps of broader significance, this work reveals a new metal-free route germane to the conversion of NOx to NH3.
- Anju, Balakrishnan S.,Kundu, Subrata,Mondal, Aditesh,Sahana, Tuhin
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supporting information
p. 20661 - 20665
(2021/08/25)
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- Accelerated reduction and solubilization of elemental sulfur by 1,2-aminothiols
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Nucleophilic 1,2-aminothiol compounds readily reduce typically-insoluble elemental sulfur to polysulfides in both water and nonpolar organic solvents. The resulting anionic polysulfide species are stabilized through hydrogen-bonding interactions with the proximal amine moieties. These interactions can facilitate sulfur transfer to alkenes.
- Stoffel, Jonathan T.,Riordan, Kimberly T.,Tsui, Emily Y.
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supporting information
p. 12488 - 12491
(2021/12/04)
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- Synthesis of ArCF2X and [18F]Ar-CF3via Cleavage of the Trifluoromethylsulfonyl Group
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A versatile synthesis of ArCF2X and [18F]Ar-CF3 type compounds from readily available ArCF2SO2CF3 has been developed. Diverse nucleophiles, including weak nucleophiles such as halides (18F-, Cl-, Br-, and I-), RSH, and ROH, could react with ArCF2SO2CF3 efficiently to give the corresponding difluoromethylene products. The control experiments and the Hammett plot indicated that the reaction might proceed through a difluorocarbocation intermediate generated from the steric hindrance-assisted cleavage of the trifluoromethylsulfonyl group.
- Gao, Xinyan,Gong, Kehao,Han, Junbin,Wang, Juan,Wang, Mingwei,Xu, Bo,Yang, Ren-Yin,Zeng, Xiaojun
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supporting information
(2021/12/17)
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- Preparation method of diaryl disulfide
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The invention relates to a preparation method of diaryl disulfide. The method comprises the following steps: reacting halogenated aromatic hydrocarbon with magnesium powder to generate a Grignard reagent, adding sulfur powder, and carrying out a reaction under the action of an acid and an oxidant to obtain the diaryl disulfide. The aromatic disulfide is synthesized by using the cheap and easily available halogenated aromatic hydrocarbon as a synthesis raw material, and then reacts with the magnesium powder to generate the Grignard reagent, and the Grignard reagent reacts with the sulfur powderunder the action of the acid and the oxidant to obtain the diaryl disulfide. The whole method has the advantages of realization of direct synthesis without heavy metal catalysis or complex ligands inthe process and midway discharging, environmental friendliness, high conversion rate, high yield, high purity, simple process, convenience in operation, and suitableness for large-scale production.
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Paragraph 0055-0057; 0064-0065
(2020/02/29)
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- DABCO-promoted Diaryl Thioether Formation by Metal-catalyzed Coupling of Sodium Sulfinates and Aryl Iodides
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A scalable catalytic synthesis method using commodity chemicals for constructing diaryl thioethers directly from sodium arylsulfinates and iodoarenes is reported in this study. In the presence of CuO or other copper salts such as Cu(OAc)2 as well as palladium catalysts, DABCO demonstrated to be essential to promote this transformation. Various iodoarenes and aryl sulfinates were examined and demonstrated the viability of this method. The mechanistic study showed that radical reactions occurred, while DABCO N-oxide radical can be observed by mass spectrometry. A plausible catalytic mechanism involving DABCO is also discussed, suggesting synergistic reduction of sulfinate by Cu(II) and DABCO is the key step of this coupling reaction. (Figure presented.).
- Liu, Yanpeng,Lam, Long Yin,Ye, Jiqing,Blanchard, Nicolas,Ma, Cong
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p. 2326 - 2331
(2020/05/05)
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- Selectivity switch in the aerobic oxygenation of sulfides photocatalysed by visible-light-responsive decavanadate
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Nanometre-sized metal oxides are promising species for the development of visible-light-responsive photocatalysts for the selective transformation of organic functional groups. In this article, we report that decavanadate ([V10O28]6-, V10) behaved as an efficient visible-light-responsive photocatalyst in the product-selective oxygenation of sulfides achieved using O2 (1 atm) as the green oxidant. In particular, we revealed that visible-light-responsive photocatalysis of V10 showed remarkable activity for the oxygenation of structurally diverse sulfides to form the corresponding sulfones using O2 in methyl ethyl ketone (MEK). Furthermore, by simply adding water to the reaction mixture, the product selectivity of sulfide oxygenation can be significantly switched toward the production of sulfoxides, without concomitant loss of photocatalytic activity. Based on experimental evidence, we inferred the following mechanistic steps for this photocatalytic system: the aerobic oxygenation of sulfides to form the corresponding sulfoxides initiated by a visible-light-induced photoredox reaction of V10. As for the formation of sulfones, MEK-derived peroxide species as the co-catalysts are probably involved in the oxygenation of sulfoxides to sulfones. The selectivity switch of the V10-photocatalysed reaction brought about by water addition is most likely achieved by suppressing the formation of MEK-derived peroxide species. This journal is
- Li, Chifeng,Mizuno, Noritaka,Murata, Kei,Ishii, Kazuyuki,Suenobu, Tomoyoshi,Yamaguchi, Kazuya,Suzuki, Kosuke
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supporting information
p. 3896 - 3905
(2020/07/09)
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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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- Preparation method of diphenyl disulfide compounds
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The invention discloses a preparation method of diphenyl disulfide compounds. The preparation method comprises the following steps: stirring an isopropyl magnesium halide Grignard reagent and a substituted halogen benzene compound in an organic solvent at -78 DEG C to -20 DEG C for 30-90 minutes to obtain a thoroughly halogen-magnesium exchanged substituted phenyl Grignard reagent; and adding dichlorodisulfide into the reaction system, slowly heating to room temperature after the reaction is finished, quenching the reaction by using a saturated ammonium chloride aqueous solution, extracting byusing ethyl acetate or diethyl ether, drying by using anhydrous magnesium sulfate, and concentrating the organic phase to obtain the diphenyl disulfide compounds. According to the method, the diphenyl disulfide compounds are prepared by taking the phenyl Grignard reagent as a raw material through a one-pot method, and has the following advantages: the synthetic route is short, the preparation process is simple, the cost is low, the operation is easy, the yield is excellent, and the industrial production is easy.
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Paragraph 0038; 0039; 0040; 0041; 0042; 0043
(2020/10/21)
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- A general method for site-selective Csp3-S bond formation: Via cooperative catalysis
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Herein, we report a copper-catalysed site-selective thiolation of Csp3-H bonds of aliphatic amines. The method features a broad substrate scope and good functional group compatibility. Primary, secondary, and tertiary C-H bonds can be converted into C-S bonds with a high efficiency. The late-stage modification of biologically active compounds by this method was also demonstrated. Furthermore, the one-pot preparation of pyrrolidine or piperidine compounds via a domino process was achieved.
- Qin, Yuman,Han, Yujie,Tang, Yongzhen,Wei, Junfa,Yang, Mingyu
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p. 1276 - 1282
(2020/02/15)
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- Electrophilic Vinylation of Thiols under Mild and Transition Metal-Free Conditions
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The iodine(III) reagents vinylbenziodoxolones (VBX) were employed to vinylate a series of aliphatic and aromatic thiols, providing E-alkenyl sulfides with complete chemo- and regioselectivity, as well as excellent stereoselectivity. The methodology displays high functional group tolerance and proceeds under mild and transition metal-free conditions without the need for excess substrate or reagents. Mercaptothiazoles could be vinylated under modified conditions, resulting in opposite stereoselectivity compared to previous reactions with vinyliodonium salts. Novel VBX reagents with substituted benziodoxolone cores were prepared, and improved reactivity was discovered with a dimethyl-substituted core.
- Castoldi, Laura,Di Tommaso, Ester Maria,Gr?fen, Barbara,Olofsson, Berit,Reitti, Marcus
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supporting information
p. 15512 - 15516
(2020/06/23)
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- Extended Pummerer fragmentation mediated by carbon dioxide and cyanide
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Pummerer rearrangement reactions generate sulfur (II) oxidation state from sulfur (IV) starting materials in the presence of activating reagents. We found unprecedented transformation of vinyl sulfoxide; disulfide formation reactions mediated by atmospheric pressure of carbon dioxide in extended Pummerer rearrangement reactions. Only under CO2 atmosphere, we observed moderate to high yields of disulfide starting from sulfur (IV) starting materials. Investigations on the reaction mechanism revealed that the degradation of the starting materials and the products was significant in the absence of CO2. Further evidence for the suggested reaction mechanism was obtained by a cross-over experiment and a radical trapping reagent.
- Liu, Jian,Kragh, Rasmus R.,Kamounah, Fadhil S.,Lee, Ji-Woong
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- TBAI-mediated sulfenylation of arenes with arylsulfonyl hydrazides in DPDME
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An efficient TBAI (tetrabutylammonium iodide)-mediated C–H sulfenylation of arenes with arylsulfonyl hydrazides in dipropylene glycol dimethyl ether (DPDME) was described. Various electron-rich arenes were applicable in the reaction, such as naphthylamine, naphthol, aniline, indole, pyrrole, and imidaz o [1,2-a] pyridine. A wide range of the aryl sulfides were obtained with good functional group tolerance. This method features green reaction conditions (odorless and easily available sulfur reagent, recyclable TBAI, and DPDME as solvent), and broad substrate scope. The synthetic potential is demonstrated by gram-scale synthesis and downstream transformations. The mechanism studies show that the reaction is achieved through electrophilic substitution process, and diaryl disulfide may be the main intermediate.
- Jie, Zhang,Jing, He,Ping, Liu,Xuezhen, Li,Yali, Liu,Yueting, Wei
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- One-pot aerobic oxidative sulfonamidation of aromatic thiols with ammonia by a dual-functional β-MnO2 nanocatalyst
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High-surface-area β-MnO2 (β-MnO2-HS) nanoparticles could act as effective heterogeneous catalysts for the one-pot oxidative sulfonamidation of various aromatic and heteroaromatic thiols to the corresponding sulfonamides using molecular oxygen (O2) and ammonia (NH3) as respective oxygen and nitrogen sources, without the need for any additives.
- Hayashi, Eri,Yamaguchi, Yui,Kita, Yusuke,Kamata, Keigo,Hara, Michikazu
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supporting information
p. 2095 - 2098
(2020/02/26)
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- Sequential C-S and S-N Coupling Approach to Sulfonamides
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A one-pot three-component reaction involving nitroarenes, (hetero)arylboronic acids, and potassium pyrosulfite leading to sulfonamides was described. A broad range of sulfonamides bearing different reactive functional groups were obtained in good to excellent yields through sequential C-S and S-N coupling that does not require metal catalysts.
- Chen, Kai,Chen, Wei,Han, Bing,Chen, Wanzhi,Liu, Miaochang,Wu, Huayue
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supporting information
p. 1841 - 1845
(2020/03/04)
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- Regioselective Ortho‐C–H sulfenylation of free phenols catalyzed by Co(II)-immobilized on silica-coated magnetic nanoparticles
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Fe3O4?SiO2-UT?CoII is prepared by the silica-coated magnetic nanoparticles, urea-triazole, and CoCl2. This organic-inorganic hybride composite showed a good to excellent catalytic activity toward regioselective ortho-sulfenylation of free phenols and naphthols using pivalic anhydride as a directing group, also K2S2O8 and PPh3 were employed as oxidant and additive respectively. The newly synthesized catalyst was fully characterized by using different techniques such as FT-IR, TGA, DTG, TEM, SEM, EDS, ICP and VSM analyses. The competitive price, accessibility and lower toxicity of cobalt compared to expensive transition metals using for C–H bond activation and functionalization constitute precious advantages for this method. Moreover, this heterogeneous catalyst could be magnetically recovered and reused without significant loss of its catalytic activity after five cycles.
- Khaef, Sepideh,Khakyzadeh, Vahid,Rostami, Abed,Taherpour, Avat Arman,Yarie, Meysam,Zolfigol, Mohammad Ali
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- Intermediacy of Copper(I) under Oxidative Conditions in the Aerobic Copper-Catalyzed Decarboxylative Thiolation of Benzoic Acids
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An experimental mechanistic study of the aerobic copper-catalyzed decarboxylative thiolation of benzoic acids with arenethiols is reported. For the model reaction, the findings support the corresponding disulfide (PhSSPh) of the arenethiol (PhSH) as the active thiolating source under reaction conditions. Synthesis and reactivity studies along with kinetic measurements support the chemical and kinetic competence of catalytically active well-defined Cu complexes: (phen)CuI(O2CC6H4-o-NO2) (2), [(phen)CuI(μ-SC6H5)]2 (3), (phen)CuI(C6H4-o-NO2) (4), and (phen)CuII(O2CC6H4-o-NO2)2 (5) (phen = 1,10-phenanthroline). The presence of an induction period in the stoichiometric reaction of the copper(II) complex (phen)CuII(O2CC6H4-o-NO2)2 (5) with PhSSPh and the absence of an induction period in the analogous stoichiometric reaction of the copper(I) complex (phen)CuI(O2CC6H4-o-NO2) (2) suggest that a copper(I) carboxylate is a more likely intermediate than a copper(II) carboxylate. The observation of in situ reduction of CuII to CuI further supports CuI as the primary active catalytic species, and spectroscopic studies also indicate the catalyst resting state to be a CuI species. The catalytic reaction exhibits a first-order dependence on [CuI] and [2-nitrobenzoic acid] and a zero-order dependence on [PhSSPh] and p(O2), suggestive of turnover-limiting decarboxylation of a copper(I) carboxylate. Oxygen was found to promote the essential oxidative cleavage of the copper(I) thiolate intermediate [(phen)CuI(μ-SC6H5)]2 (3) to regenerate a catalytically active [(phen)CuII] (Cuox) species with concomitant formation of PhSSPh. On the basis of these findings, a reaction pathway is proposed for the C-S coupling reaction that includes the key CuI-based intermediates (phen)CuI(O2CC6H4-o-NO2) (2) and (phen)CuI(C6H4-o-NO2) (4). The pathway accounts for the role of O2 in generating the active thiolating source, PhSSPh, as well as enabling catalytic turnover of in situ generated [(phen)CuI(μ-SC6H5)]2 (3).
- Green, Kerry-Ann,Hoover, Jessica M.
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p. 1769 - 1782
(2020/02/06)
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- Multicomponent Synthesis of Sulfones and Sulfides from Triarylbismuthines and Sodium Metabisulfite in Deep Eutectic Solvents
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This study describes a novel and catalyst-free methodology for the multicomponent synthesis of a broad range of sulfones, disulfides, and sulfides from non-toxic triarylbismuthines (Ar3Bi) and sodium metabisulfite (Na2S2O5) in deep eutectic solvents (DESs). The fine tuning of the DESs properties allowed the solubility of all reagents, enhancing their reactivity, as well as, the recyclability of the reaction medium for at least 5 consecutive cycles. Thus, this versatile strategy uses non-toxic reagents without the need of metal catalysts in a sustainable solvent, being an interesting alternative to traditional hazardous protocols.
- Saavedra, Beatriz,Marset, Xavier,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 3462 - 3467
(2020/06/04)
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- K2S as Sulfur Source and DMSO as Carbon Source for the Synthesis of 2-Unsubstituted Benzothiazoles
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We describe a three-component reaction of o-iodoanilines with K2S and DMSO that provides 2-unsubstituted benzothiazoles in moderate to good isolated yields with good functional group tolerance. Electron-rich aromatic amines and o-phenylenediamines instead of o-iodoanilines provided 2-unsubstituted benzothiazoles and 2-unsubstituted benzimidazoles with and without K2S under similar conditions. Notably, DMSO plays three vital roles: carbon source, solvent, and oxidant.
- Deng, Guobo,Kuang, Daizhi,Liang, Yun,Yang, Yuan,Yu, Jiangxi,Zhang, Fuxing,Zhu, Xiaoming
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supporting information
p. 3789 - 3793
(2020/06/04)
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- Directed oxidative coupling of thiols in the synthesis of unsymmetrical disulfides
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Oxidative coupling of two different thiols bearing aliphatic, alicyclic, aromatic, and hetero-aromatic moieties promoted by mild oxidizing agents, viz., sterically hindered o-benzo(imino)-quinones, carried out in N-methylpyrrolidone at room temperature led to unsymmetrical disulfides. Among the studied oxidizers, the most active was 3,6-di-tert-butyl-o-benzoquinone, which, in contrast to 3,5-di-tert-butyl-o-benzoquinone, was not involved in the Michael addition. Under the optimal reaction conditions, the yields of the target unsymmetrical disulfides reach 81%.
- Berberova, N. T.,Burmistrova, D. A.,Smolyaninov, I. V.
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p. 990 - 995
(2020/06/17)
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- The biothiol-triggered organotrisulfide-based self-immolative fluorogenic donors of hydrogen sulfide enable lysosomal trafficking
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Biothiol-reactive organotrisulfide-based self-immolative fluorogenic donors of H2S are rationally designed for the efficient monitoring of intracellular and lysosomal trafficking of H2S with a concomitant turn-on fluorescence. The non-toxic nature of the donors with a sustained release of H2S will certainly be helpful for their biomedical applications in the future.
- Mahato, Sulendar K.,Bhattacherjee, Debojit,Bhabak, Krishna P.
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supporting information
p. 7769 - 7772
(2020/07/27)
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- Application of Ni-based metal-organic framework as heterogeneous catalyst for disulfide addition to acetylene
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Several recent studies have shown unique adsorption activity of metal organic frameworks (MOFs) towards unsaturated hydrocarbons. In the current article, we explored the application of Ni-MOFs for S-functionalization of acetylene. We showed that Ni-MOF-74 catalyzed the reaction of disulfide addition to gaseous acetylene with excellent selectivity. The prime advantage of the proposed Ni-MOF-74 over other examined catalysts was its easy separation and recycling possibility. Moreover, it demonstrated no leaching of Ni species into the solution. The work was supplemented with a study on the catalyst behavior in the course of the reaction by using SEM, EDX, XRD, and FT-IR methods.
- Ananikov, Valentine P.,Degtyareva, Evgeniya S.,Erokhin, Kirill S.
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- Preparation method for symmetric diaryl disulfide
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The invention discloses a preparation method for symmetric diaryl disulfide. The preparation method comprises the following steps: using aromatic hydrocarbon as shown in a general formula (I) as a rawmaterial and reacting with chlorosulfonic acid to generate aryl chlorosulfonic acid, and reacting with sulfoxide chloride to synthesize aryl sulfonyl chloride as shown in a general formula (II); andpreparing the symmetric diaryl disulfide as shown in a general formula (III) under the action of a reducing agent through a reduction reaction by the aryl sulfonyl chloride as shown in the general formula (II). The disclosed preparation method for the symmetric diaryl disulfide has many advantages of low toxicity of the reaction raw material, short reaction time, cheap reagents and easy acquisition, convenient separation and purification and the like, and has very high application value and industrial production value.
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- Method for preparing 4-benzoyl-4'-methyl-diphenyl sulfide
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The invention relates to a preparation method of a photoinitiator 4-benzoyl-4'-methyl-diphenyl sulfide, in particular to a method for preparing phenyl sulfenyl chloride by taking benzene, sulfur monochloride and chlorine as raw materials, then carrying out thioetherification reaction with toluene, and finally carrying out acylation reaction with benzoyl chloride. According to the preparation method of the 4-benzoyl-4'-methyl-diphenyl sulfide provided by the invention, the shortcomings of an existing method are avoided, the used raw materials are cheap and easy to obtain, the reaction conditions are mild, the method is easy to operate, the yield is high, the cost is low, and the method is suitable for industrial stable production.
- -
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Paragraph 0028; 0029; 0030
(2019/05/22)
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- NH4I/1,10-phenanthroline catalyzed direct sulfenylation of N-heteroarenes with ethyl arylsulfinates
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An efficient synthesis of N-heterocyclic aryl sulfides via NH4I/1,10-phenanthroline-catalyzed direct sulfenylation reactions was reported. In this reaction, heteroarenes such as indoles, and pyrroles serve as nucleophiles by installing a arylthio group at the C3 and C2 position of heterocycles, respectively. With readily accessible and free of unpleasant odor ethyl arylsulfinates as sulfur reagents, the metal-free-catalyzed direct sulfenylation of N-heteroarenes has been developed. 3-Arylthio-indoles and 2-arylthio-pyrroles derivatives were obtained in moderate to excellent yields, even on gram scale. The reaction was general for a broad scope of substrates and demonstrated good tolerance to a variety of functional groups.
- Chen, Lingjuan,Zhang, Jun,Wei, Yueting,Yang, Zhen,Liu, Ping,Zhang, Jie,Dai, Bin
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- Integration of a Four-Step Reaction into One-Pot under the Coexistence of Silica-Gel-Supported Acid and Base Reagents: Synthesis of Benzo- and Naphthothiophenes Using NaHSO 4 /SiO 2 and Na 2 CO 3 /SiO 2
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A four-step synthesis of benzo- and naphthothiophenes that have biological importance and application in material science was integrated into a one-pot reaction by using silica gel-supported acid and base reagents, NaHSO 4 /SiO 2 and Na 2 CO 3 /SiO 2. The supported reagents provided acid and base environments on the surface of the supports without neutralization and worked separately in the same medium. The four-step reaction comprises (i) deacetylation of 3-halo-2,4-pentanediones to α-halo ketones, (ii) deacetylation of S -aryl thioacetates to arenethiols, (iii) coupling of α-halo ketones and arenethiols to give α-sulfanyl ketones, and (iv) cyclization of sulfanyl ketones to benzo- and naphthothiophenes. The steps (i) and (iii) proceeded by Na 2 CO 3 /SiO 2, and (ii) and (iv) by NaHSO 4 /SiO 2. The four-step reaction proceeded efficiently by introduction of starting materials and reagents in a single reaction vessel. The starting materials were very easy to handle and unpleasant smell of aryl thiols that were used in conventional methods could be avoided. Novel thirty-nine benzo- and naphthothiophenes were synthesized by this method in excellent to fair yields.
- Aoyama, Tadashi,Hayakawa, Mamiko,Kosuge, Masayuki,Nakaoka, Kyohei,Ouchi, Akihiko
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p. 2572 - 2578
(2019/06/08)
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- Utilizing 2-phenylpropanal as coupling partner for C-S bond formation via sequential thioarylation and decarbonylation process: A novel strategy for the synthesis of aryl alkyl sulfides
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In this study, first direct access to aryl alkyl sulfides employing 2-phenylpropanal as coupling partner is reported. Diaryl disulfides react with this aldehyde in the presence of morpholine and produce the corresponding sulfide products in high yields. In another part, disulfides are in situ generated in the reaction mixture from aryl halides/CuI/Cyanodithioformate and coupled with 2-phenylpropanal to access aryl alkyl sulfides.
- Shaikhi Shahidzadeh, Elham,Nowrouzi, Najmeh,Abbasi, Mohammad
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- NiFe2O4 as a magnetically recoverable nanocatalyst for odourless C–S bond formation via the cleavage of C–O bond in the presence of S8 under mild and green conditions
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We present green methodologies for one-pot and odourless syntheses of unsymmetric and symmetric diaryl sulfides via C─O bond activation using NiFe2O4 magnetic nanoparticles as a reusable heterogeneous nanocatalyst. The synthesis of unsymmetric sulfides is performed using the cross-coupling reaction of phenolic esters such as acetates, triflates and tosylates with arylboronic acid/S8 or triphenyltin chloride/S8 as thiolating agents in the presence of base and NiFe2O4 magnetic nanoparticles as a catalyst in poly(ethylene glycol) as solvent at 60–85°C. Also, the synthesis of symmetric diaryl sulfides from phenolic compounds using S8 as the sulfur source and NiFe2O4 as catalyst in dimethylformamide at 120°C is described. Using these protocols, the syntheses of various unsymmetric and symmetric sulfides become easier than using the available protocols due to the use of a magnetically reusable bimetallic nanocatalyst and avoiding the use of thiols and aryl halides.
- Atashkar, Bahareh,Rostami, Amin,Rostami, Abed,Zolfigol, Mohammad Ali
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- Synthesis of 2D and 3D MOFs with tuneable Lewis acidity from preformed 1D hybrid sub-domains
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Novel MOF-type materials with different morphologies based on assembled 1D organic-inorganic sub-domains were prepared using specific monodentate benzylcarboxylate spacers with functional substituents in the para-position as structure modulating agents. T
- Moreno, José María,Velty, Alexandra,Díaz, Urbano,Corma, Avelino
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p. 2053 - 2066
(2019/02/20)
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- Metal free, facile sulfenylation of ketene dithioacetals catalyzed by an HBr-DMSO system
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A transition metal free, highly efficient, sulfenylation of ketene dithioacetals catalyzed by an HBr-DMSO system is achieved. This strategy employs inexpensive and readily available HBr and DMSO to provide a direct C-H bond sulfenylation with a broad rang
- Sorabad, Ganesh Shivayogappa,Maddani, Mahagundappa Rachappa
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supporting information
p. 5996 - 6000
(2019/04/16)
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- Metal-free regioselective direct thiolation of 2-pyridones
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A highly regioselective metal-free direct C-H thiolation of 2-pyridones with disulfides or thiols has been developed. A combination of persulfate and a commercially available halide source such as LiCl, NCS or I2 enables the successful direct incorporation of a sulfide moiety into the 5-position of pyridone under mild conditions, providing a useful and convenient approach for the preparation of a diverse array of 5-thio-substituted pyridones in moderate to excellent yields.
- Phakdeeyothin, Kunita,Yotphan, Sirilata
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p. 6432 - 6440
(2019/07/09)
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- An efficient clean methodology for the C-S coupling to aryl thioethers and S-S homocoupling to aromatic disulfides catalyzed over a Ce(IV)-leucine complex immobilized on mesoporous MCM-41
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A novel Ce(iv)-anchored l-leucine covalently bonded to mesoporous MCM-41 has been synthesized by a non-hydrothermal post-functionalization approach. It has been thoroughly characterized by sophisticated physicochemical techniques. The material was applied in the efficient green synthesis of aromatic sulfides by C-S coupling using molecular sulfur and haloarenes. Another catalytic application was in the synthesis of symmetric disulfides by the homocoupling of aromatic thiols in the presence of H2O2 as an oxidant. The ligand-free protocol is simple, clean and free from hazardous chemicals. Moreover, the catalyst is reusable for several times, thus making the methodology sustainably viable.
- Veisi, Hojat,Tamoradi, Taibeh,Karmakar, Bikash
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p. 10343 - 10351
(2019/07/09)
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- Universal Anticancer Cu(DTC)2 Discriminates between Thiols and Zinc(II) Thiolates Oxidatively
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Aerobic organisms must rely on abundant intracellular thiols to reductively protect various vital functional units, especially ubiquitous zinc(II) thiolate sites of proteins, from deleterious oxidations resulting from oxidizing environments. Disclosed here is the first well-defined model study for reactions between zinc(II) thiolate complexes and copper(II) complexes. Among all the studied ligands of copper(II), diethyldithiocarbamate (DTC) displays a unique redox-tuning ability that enables copper(II) to resist the reduction by thiols while retaining its ability to oxidize zinc(II) thiolates to form disulfides. This work proves for the first time that it is possible to develop oxidants to discriminate between thiols and zinc(II) thiolates, alluding to a new chemical principle for how oxidants, especially universal anticancer Cu(DTC)2, might circumvent the intracellular reductive defense around certain zinc(II) thiolate sites of proteins to kill malignant cells.
- Xu, Luyan,Xu, Jialin,Zhu, Jingwei,Yao, Zijian,Yu, Na,Deng, Wei,Wang, Yu,Lin, Bo-Lin
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p. 6070 - 6073
(2019/03/29)
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- Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
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A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
- Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
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p. 3048 - 3055
(2019/03/21)
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- Reactions between 5-Nitroso-1,3-diphenyltetrazolium salts and electron-rich arenes, amines, thiophenol, sulfoxides, and thioanisole
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A series of reactions between 5-nitroso-1,3-diphenyltetrazo-lium tetrafluoroborate and methoxybenzenes, amines, thiols, sulfoxides, and sulfides, most of which are generally accepted as being inert to nitroso groups, is reported here. The tetrazolium-activated nitroso functionality is capable of oxidizing the aforementioned substrates to give the corresponding oxidized products, and the nitroso tetrazolium itself is transformed into the corresponding amide or hydroxyamide, depending on the nature of the reaction partners. In the case of thioanisole, an addition product was obtained.
- Matsukawa, Yuta,Hirashita, Tsunehisa,Araki, Shuki
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supporting information
p. 540 - 544
(2019/04/05)
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- Mechanistic and experimental study on copper-catalyzed C3-sulfenylation of indoles with sulfur powder and aryl iodides
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The copper-catalyzed sulfenylation of indoles with aryl iodide and sulfur powder has been investigated both experimentally and theoretically. This protocol provides a direct and facile approach to prepare 3-sulfenylindoles with moderate to excellent yields and good functional-group tolerance. The in-situ IR analysis provided evidence for that NaOAc could promote the synthesis of diphenyl disulfide by the coupling of aryl iodide and sulfur powder. According to DFT calculations, the coupling pathway involving the intermediate N-methyl-3-iodoindole is more favored than the direct coupling by the C–H activation of indole. The N-methyl-3-iodoindole was identified as a crucial intermediate in the catalytic cycle.
- Ge, Xin,Cheng, Lin,Sun, Fengli,Liu, Xuemin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
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