- Discovery of a novel family of FKBP12 “reshapers” and their use as calcium modulators in skeletal muscle under nitro-oxidative stress
-
The hypothesis of rescuing FKBP12/RyR1 interaction and intracellular calcium homeostasis through molecular “reshaping” of FKBP12 was investigated. To this end, novel 4-arylthioalkyl-1-carboxyalkyl-1,2,3-triazoles were designed and synthesized, and their e
- Aizpurua, Jesus M.,Miranda, José I.,Irastorza, Aitziber,Torres, Endika,Eceiza, Maite,Sagartzazu-Aizpurua, Maialen,Ferrón, Pablo,Aldanondo, Garazi,Lasa-Fernández, Haizpea,Marco-Moreno, Pablo,Dadie, Naroa,López de Munain, Adolfo,Vallejo-Illarramendi, Ainara
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- Synthesis, characterization and antibacterial activity of the thioether linked 1,2,3-triazoles
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A green synthetic approach for the expedite construction of thirty six thioether linked 1,2,3-triazoles was carried out using Cellulose supported CuI nanoparticles in water. The structure of synthesized triazoles was explicated by spectroscopic techniques
- Kaushik, Chander P.,Sangwan, Jyoti
-
supporting information
p. 3403 - 3415
(2021/09/13)
-
- Electrophilic Chlorine from Chlorosulfonium Salts: A Highly Chemoselective Reduction of Sulfoxides
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Herein, we describe a selective late-stage deoxygenation of sulfoxides based on a novel application of chlorosulfonium salts and demonstrate a new process using these species generated in situ from sulfoxides as the source of electrophilic chlorine. The use of highly nucleophilic 1,3,5-trimethoxybenzene (TMB) as the reducing agent is described for the first time and applied in the deoxygenation of simple and functionalized sulfoxides. The method is easy to handle, economic, suitable for gram-scale operations, and readily applied for poly-functionalized molecules, as demonstrated with more than 45 examples, including commercial medicines and analogues. We also report the results of competition experiments that define the more reactive sulfoxide and we present a mechanistic proposal based on substrate and product observations.
- Acosta-Guzmán, Paola,Mahecha-Mahecha, Camilo,Gamba-Sánchez, Diego
-
supporting information
p. 10348 - 10354
(2020/07/13)
-
- Direct Decarboxylative Allylation and Arylation of Aliphatic Carboxylic Acids Using Flavin-Mediated Photoredox Catalysis
-
We describe herein a direct decarboxylative allylation of aliphatic carboxylic acids with allylsulfones using visible light and riboflavin tetraacetate (RFTA) as photocatalyst. The reaction proceeds at room temperature tolerating a wide range of functiona
- Ramirez, Nieves P.,Lana-Villarreal, Teresa,Gonzalez-Gomez, Jose C.
-
supporting information
p. 1539 - 1550
(2019/08/07)
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- Photochemical Doyle-Kirmse Reaction: A Route to Allenes
-
This Letter describes the metal-free, blue-light-induced [2,3]-sigmatropic rearrangement of sulfonium ylides generated from donor/acceptor diazoalkanes and propargyl sulfides. The reaction furnishes highly functionalized allenes from a broad range of starting materials in decent yield. Mechanistic experiments supported by the literature data suggest singlet carbenes as intermediates in this reaction.
- Or?owska, Katarzyna,Rybicka-Jasińska, Katarzyna,Krajewski, Piotr,Gryko, Dorota
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supporting information
p. 1018 - 1021
(2020/01/31)
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- Iron-Mediated Cyclization of 1,3-Diynyl Propargyl Aryl Ethers with Dibutyl Diselenide: Synthesis of Selenophene-Fused Chromenes
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The synthesis of selenophene-fused chromene derivatives starting from 1,3-diynyl propargyl aryl ethers is reported herein. The method is based on carbon-carbon, carbon-selenium, selenium-carbon and carbon-selenium bonds formation in a one-pot protocol, using iron(III) chloride and dibutyl diselenide as promoters. The same reaction conditions were applied to propargyl anilines leading to the formation of 1-(butylselanyl)-selenophene quinolines. The results showed that the dilution and temperature of substrate addition had a crucial influence in the products obtained. When the substrates were added at room temperature, in the absence of a solvent, a mixture of products was obtained, whereas the slowly addition (15 min) of starting materials, as a dichloromethane solution, at 0 °C led to the product formation in good yields. The mechanistic study indicates that the cooperative action between iron(III) chloride and dibutyl diselenide was essential to promote the cyclization, whereas separately none of them was effective in promoting the cyclization. We proved the synthetic utility of heterocycles obtained in the Suzuki cross coupling reaction, giving the corresponding cross-coupled products in good yields. In addition, the organoselenium moiety was removed from the structures of products by using n-butyllithium. (Figure presented.).
- Back, Davi F.,Lutz, Guilherme,Zeni, Gilson
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p. 1096 - 1105
(2020/01/25)
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- Gold-Catalyzed Oxidative Hydrative Alkenylations of Propargyl Aryl Thioethers with Quinoline N-Oxides Involving a 1,3-Sulfur Migration
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This work reports gold-catalyzed oxidative alkenylations of quinoline N-oxides with propargyl aryl thioethers to afford 3-hydroxy-1-alkylidenephenylthiopropan-2-one via a 1,3-sulfur group migration. The mechanism of this reaction is postulated to involve
- Wagh, Sachin Bhausaheb,Singh, Rahulkumar Rajmani,Sahani, Rajkumar Lalji,Liu, Rai-Shung
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supporting information
p. 2755 - 2758
(2019/04/30)
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- Convenient synthesis, antimalarial and antimicrobial potential of thioethereal 1,4-disubstituted 1,2,3-triazoles with ester functionality
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This paper elicits the synthesis of twenty five 1,4-disubstituted 1,2,3-triazole analogs (5a–5y) comprising thioether and ester linkages from aryl(prop-2-yn-1-yl)sulfanes and benzyl 2-azidoacetates employing Cu(I) catalyzed Huisgen 1,3-dipolar cycloaddition. Structures of synthesized compounds were elucidated by spectroscopic techniques like FTIR, 1H NMR, 13C NMR, and HRMS. Newly synthesized compounds were screened for in vitro antimalarial evaluation against P. falciparum strain and microbicidal potential against B. subtilis, S. epidermidis, E. coli, P. aeruginosa, C. albicans, and A. niger. Some of synthesized triazoles displayed moderate antimalarial activity against tested strain, while, the compounds 5i and 5n were found to exhibit significant inhibitory activity against most of the tested microbial strains.
- Kaushik,Pahwa, Ashima
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p. 458 - 469
(2017/10/13)
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- 1-D copper(I) coordination polymer based on bidentate 1,3-dithioether ligand: Novel catalyst for azide-alkyne-cycloaddition (AAC) reaction
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A novel 1,3-bis(4-fluorophenylthio)-propane ligand based CuI 1-D polymeric coordination complex having formula ([(CuI)2{ArS(CH2)3SAr}2]n, Ar = 4-F-C6H4) has been synthesized and characterized by 1H NMR, 13C NMR and single crystal XRD techniques. This complex has been employed for the first time as suitable catalyst for base-free one-pot three-component regioselective azide-alkyne cycloaddition (AAC) reaction. A novel 1,2,3-triazole compound with sulfur functionalized pendant arms has also been prepared using our catalytic system in a multicomponent manner via one-pot two-step reaction.
- Saha, Sankar,Biswas, Kinkar,Basu, Basudeb
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supporting information
p. 2541 - 2545
(2018/05/28)
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- Sulfinate-Organocatalyzed (3+2) Annulation Reaction of Propargyl or Allenyl Sulfones with Activated Imines
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An operationally simple methodology for the synthesis of 4-sulfonyl-3-pyrrolines is described using a propargylic sulfone and N-sulfonyl imines as substrates. This annulation process is initiated by an arenesulfinate organocatalyst, which allows a smooth isomerization of the alkynyl precursor into the corresponding allene, followed by the generation of a highly reactive allyl sulfone anion. An asymmetric version involving an unprecedented enantiopure sulfinate–ammonium cooperative ion pair (PhSO2– R4N+*) was investigated. A proof-of-concept, with enantiomeric excesses of up to 41 %, was obtained according to a preliminary screening of commercially available chiral phase-transfer catalysts.
- Martzel, Thomas,Lohier, Jean-Fran?ois,Gaumont, Annie-Claude,Brière, Jean-Fran?ois,Perrio, Stéphane
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supporting information
p. 5069 - 5073
(2018/09/14)
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- Regioselective synthesis and antimicrobial evaluation of some thioether–amide linked 1,4-disubstituted 1,2,3-triazoles
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A series of 1,4-disubstituted 1,2,3-triazoles having thioether as well as amide linkage were synthesized from aryl(prop-2-yn-1-yl)sulfanes and 2-azido-N-substituted acetamides through Cu(I) catalyzed click reaction. Structures of newly synthesized compounds (3a–3x) were confirmed by spectral techniques like FTIR,1H NMR,13C NMR, and HRMS. The synthesized triazoles were evaluated for in vitro antimicrobial activity against Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae, Staphylococcus aureus, Candida albicans, and Aspergillus niger. Compounds 3m and 3q displayed appreciable broad spectrum antimicrobial activity against tested microbial strains. The nanoformulations of compounds 3m and 3q were also prepared and examined against one bacterial strain and one fungal strain.
- Kaushik,Pahwa, Ashima,Thakur, Rajesh,Kaur, Pawan
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supporting information
p. 368 - 378
(2017/02/10)
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- Aqueous hemin catalyzed sulfonium ylide formation and subsequent [2,3]-sigmatropic rearrangements
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A mild hemin catalytic system for sulfonium ylide generation via a metal carbenoid and a subsequent [2,3]-sigmatropic rearrangement reaction in aqueous solvent is well-established, with the assistance of cyclodextrin (CD) and Triton X-100. The protocol displays high catalytic activity with a broad substrate scope of aryl/alkyl allyl sulfides and diazo reagents, affording homoallyl sulfide products in up to 99% yield. Notably, this catalytic system is successful for water-insoluble allyl sulfides but ineffective for allyl amines or allyl ethers. Moreover, an unprecedented cascade reaction of sulfonium ylide formation, [2,3]-sigmatropic rearrangement and C-H insertion was reported.
- Xu, Xiaofei,Li, Chang,Tao, Zhihao,Pan, Yuanjiang
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supporting information
p. 1245 - 1249
(2017/08/15)
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- Benzenesulfonamides Incorporating Flexible Triazole Moieties Are Highly Effective Carbonic Anhydrase Inhibitors: Synthesis and Kinetic, Crystallographic, Computational, and Intraocular Pressure Lowering Investigations
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Herein we report the synthesis of two series of benzenesulfonamide containing compounds that incorporate the phenyl-1,2,3-triazole moieties. We explored the insertion of appropriate linkers, such as ether, thioether, and amino type, into the inner section
- Nocentini, Alessio,Ferraroni, Marta,Carta, Fabrizio,Ceruso, Mariangela,Gratteri, Paola,Lanzi, Cecilia,Masini, Emanuela,Supuran, Claudiu T.
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p. 10692 - 10704
(2016/12/16)
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- Click-tailed coumarins with potent and selective inhibitory action against the tumor-associated carbonic anhydrases IX and XII
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Coumarins behave as inhibitors of the metalloenzyme carbonic anhydrase (CA, EC 4.2.1.1) with a mechanism of inhibition distinct from other classes of inhibitors. A series of 7-substituted coumarins incorporating aryl-triazole moieties were prepared by click chemistry procedures starting from 7-hydroxycoumarin or 4-methyl-7-aminocoumarin. The panel of new compounds was assayed for the inhibition of the cytosolic, widespread human (h) isoforms hCA I and II, and the transmembrane, tumor-associated ones hCA IX and XII. Most of the coumarins were weak inhibitors or did not inhibit significantly hCA I and II, but showed low nanomolar inhibitory action against the transmembrane isoforms (KI of 14.3-34.4 nM against hCA IX and of 4.7-37.8 nM against hCA XII). Since many hypoxic tumors overexpress hCA IX/XII, and as these targets were recently validated for obtaining antitumor/antimetastatic agents, with one inhibitor in Phase I clinical trials, the present findings constitute an interesting extension to the knowledge of non-sulfonamide, selective inhibitors of CA isoforms involved in serious pathologies.
- Nocentini, Alessio,Carta, Fabrizio,Ceruso, Mariangela,Bartolucci, Gianluca,Supuran, Claudiu T.
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p. 6955 - 6966
(2015/11/11)
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- Oxo-rhenium(V) complexes containing heterocyclic ligands as catalysts for the reduction of sulfoxides
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This work reports the catalytic activity of a large variety of oxo-rhenium(V) complexes (1 mol-%) containing the ligands 2-(2-hydroxy-5- methylphenyl)benzotriazole (Hhmpbta), 2-(2-hydroxyphenyl)benzothiazole (Hhpbt), 2-(2-hydroxyphenyl)benzoxazole (Hhpbo), and 2-(2-hydroxyphenyl)-1H-benzimidazole (Hhpbi) in the deoxygenation of sulfoxides with silanes or boranes as the reducing agents. In general, all of the complexes are excellent catalysts, although the PhSiH3/[ReOBr2(hmpbta)(PPh3)] and pinacolborane/[ReOBr2(hmpbta)(PPh3)] systems are the most efficient for the reduction of aromatic and aliphatic sulfoxides and tolerate different functional groups. Copyright
- Sousa, Sara C. A.,Bernardo, Joana R.,Wolff, Mariusz,Machura, Barbara,Fernandes, Ana C.
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p. 1855 - 1859
(2014/04/03)
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- Oxo-Rhenium(V) Complexes Containing Heterocyclic Ligands as Catalysts for the Reduction of Sulfoxides
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This work reports the catalytic activity of a large variety of oxo-rhenium(V) complexes (1 mol-%) containing the ligands 2-(2-hydroxy-5-methylphenyl)benzotriazole (Hhmpbta), 2-(2-hydroxyphenyl)benzothiazole (Hhpbt), 2-(2-hydroxyphenyl)benzoxazole (Hhpbo), and 2-(2-hydroxyphenyl)-1H-benzimidazole (Hhpbi) in the deoxygenation of sulfoxides with silanes or boranes as the reducing agents. In general, all of the complexes are excellent catalysts, although the PhSiH3/[ReOBr2(hmpbta)(PPh3)] and pinacolborane/[ReOBr2(hmpbta)(PPh3)] systems are the most efficient for the reduction of aromatic and aliphatic sulfoxides and tolerate different functional groups.
- Sousa, Sara C. A.,Bernardo, Joana R.,Wolff, Mariusz,Machura, Barbara,Fernandes, Ana C.
-
supporting information
p. 1855 - 1859
(2015/10/05)
-
- Facile One-Pot Synthesis of 1,2,3-Triazoles Featuring Oxygen, Nitrogen, and Sulfur Functionalized Pendant Arms
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A practical and efficient one-pot synthesis of novel 1,2,3-triazoles featuring nitrogen, oxygen, and sulfur functionalized pendant arms has been developed. The click reaction of mono-propargyl derivatives supported by aniline, thiophenol, and benzyl alcohol, with sodium azide and p-substituted benzyl halogenides, renders a series of N-substituted-1,2,3-triazoles in good yields under mild reaction conditions. The catalyst system was based in Cu(OAc)2·H2O, sodium L-ascorbate, and 1,10-phenanthroline monohydrate, and all reactions were performed in a mixture H2O-ethanol (4:1 v/v). Additionally, the preparation of bis-1,2,3-triazoles supported by di-propargylated aniline was carried out, demonstrating the versatility of the present methodology. [Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for the following free supplemental resource(s): Full experimental and spectral details.]
- Mendoza-Espinosa, Daniel,Negron-Silva, Guillermo,Lomas-Romero, Leticia,Gutierrez-Carrillo, Atilano,Santillan, Rosa
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p. 807 - 817
(2014/03/21)
-
- Synthesis and biological evaluation of 4-(1,2,3-triazol-1-yl)coumarin derivatives as potential antitumor agents
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In this research, a series of 4-(1,2,3-triazol-1-yl)coumarin conjugates were synthesized and their anticancer activities were evaluated in vitro against three human cancer cell lines, including human breast carcinoma MCF-7 cell, colon carcinoma SW480 cell and lung carcinoma A549 cell. To increase the biological potency, structural optimization campaign was conducted focusing on the C-4 position of 1,2,3-triazole and the C-6, C-7 positions of coumarin. In addition, to further evaluate the role of 1,2,3-triazole and coumarin for antiproliferative activity, 9 compounds possessing 4-(piperazin-1-yl)coumarin framework and 3 derivatives baring quinoline core were also synthesized. By MTT assay in vitro, most of the compounds display attractive antitumor activities, especially 23. Further flow cytometry assays demonstrate that compound 23 exerts the antiproliferative role through arresting G2/M cell-cycle and inducing apoptosis.
- Zhang, Wenjuan,Li, Zhi,Zhou, Meng,Wu, Feng,Hou, Xueyan,Luo, Hao,Liu, Hao,Han, Xuan,Yan, Guoyi,Ding, Zhenyu,Li, Rui
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supporting information
p. 799 - 807
(2014/02/14)
-
- Rh(II)-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides
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In this paper, Rh2(OAc)4-catalyzed [2,3]-sigmatropic rearrangement of sulfur ylides derived from N-tosylhydrazones and sulfides is reported. A series of tosylhydrazones derived from aldehydes were successfully used for [2,3]-sigmatropic rearrangement by reaction with either allylic phenyl sulfides or propargyl phenyl sulfides. The reaction conditions were optimized and afforded the products in moderate to good yields. In addition, a novel and convenient approach for the synthesis of cyclobutenones and cyclopropanes has been developed through direct oxidation of the rearrangement products.
- Li, Yuye,Huang, Zhongxing,Wu, Xinhu,Xu, Peng-Fei,Jin, Jing,Zhang, Yan,Wang, Jianbo
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experimental part
p. 5234 - 5240
(2012/08/07)
-
- Highly efficient gold nanoparticle catalyzed deoxygenation of amides, sulfoxides, and pyridine N-oxides
-
Selective deoxygenation is one of the most important reactions in the areas of total synthesis, biological chemistry, and transformation of renewable biomass resources.To date, many useful methods for the selective deoxygenation of oxygen-containing organic molecules, such as amides, nitro compounds, epoxides, sulfoxides, and those with Noxide groups, have been developed. However, these methods often include stoichiometric reactions. Some successful catalysts have been reported,but most of them are homogeneous systems and still suffer from low activities and selectivities, harsh reaction conditions, and tedious workup procedures. Therefore, further development of highly efficient heterogeneous catalysts for selective deoxygenations is highly desired.
- Mikami, Yusuke,Noujima, Akifumi,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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experimental part
p. 1768 - 1772
(2011/03/21)
-
- Reduction of sulfoxides catalyzed by oxo-complexes
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This work reports the catalytic activity of the oxo-complexes HReO 4, MoO2(acac)2, WO2Cl2, and VO(acac)2 in the reduction of sulfoxides with PhSiH3 or HBcat. The results obtained showed that the catalyst systems PhSiH 3/HReO4 (5 mol %) and HBcat/HReO4 (5 mol %) are highly efficient for the deoxygenation of sulfoxides. The complex MoO 2(acac)2 was also efficient, but the reactions required more time and heating. Finally, the complexes WO2Cl2 and VO(acac)2 showed a moderate activity.
- Cabrita, Ivania,Sousa, Sara C.A.,Fernandes, Ana C.
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experimental part
p. 6132 - 6135
(2010/12/24)
-
- Synthesis and spectroscopic study of diphenylamino-substituted phenylene-(poly)ethynylenes: remarkable effect of acetylenic conjugation modes
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A series of diphenylamino-substituted phenylene-(poly)ethynylenes were successfully synthesized by a combination of Sonogashira coupling and double elimination protocol of β-substituted sulfones. When UV-light was irradiated, the amino-substituted phenylene-(poly)ethynylene emitted strong luminescence. The emission underwent a large bathochromic shift in polar solvent because of stabilization of their charge-separated excited states. Analyses of fluorescence life times of aminoacetylenes revealed that radiationless process was suppressed in the polar solvent CH2Cl2, resulting in high quantum yields.
- Fang, Jing-Kun,An, De-Lie,Wakamatsu, Kan,Ishikawa, Takeharu,Iwanaga, Tetsuo,Toyota, Shinji,Matsuo, Daisuke,Orita, Akihiro,Otera, Junzo
-
supporting information; experimental part
p. 917 - 920
(2010/05/03)
-
- Synthesis and spectroscopic study of phenylenee (poly) ethynylenes substituted by amino or amino/cyano groups at terminal(s):Electronic effect of cyano group on charge-transfer excitation of acetylenic φ-systems
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To gain insight into substituent electronic effect on charge-transfer excitation of acetylenic p-systems, phenylenee(poly)ethynylenes substituted by Ph2N or Ph2N/cyano groups were synthesized by combination of Sonogashira coupling and double elimination protocol of b-substituted sulfones.These substituted phenyleneethynylenes showed large molar absorption coefficients 3, and emitted strong fluorescence upon UV light irradiation.Phenylenee(poly)ethynylenes, which involve butadiyne or hexatriyne motifs, emitted fluorescence in remarkably lower fluorescence quantum yields FF as their polyethynylene motifs e(C^C)ne expanded.The drastic decrease of fluorescence quantum yields FF were explained in terms of increasing nonradiative reaction rate constants knr, which had been determined by the corresponding fluorescence quantum yields F F and lifetime values s.The emission underwent a large bathochromic shift in polar solvents because the charge-separated excited state is more stabilized than the ground state.Comparison of slope values r in Lippert/Mataga plot for the Ph2N and Ph2N/cyano-substituted phenylenee(poly)ethynylenes revealed that the latter underwent large change of dipole moments upon photo-excitation although highly expanded acetylenic p-systems with cyano group did little.
- Fang, Jing-Kun,An, De-Lie,Wakamatsu, Kan,Ishikawa, Takeharu,Iwanaga, Tetsuo,Toyota, Shinji,Akita, Shin-Ichi,Matsuo, Daisuke,Orita, Akihiro,Otera, Junzo
-
supporting information; experimental part
p. 5479 - 5485
(2010/08/19)
-
- Highly efficient and chemoselective reduction of sulfoxides using the system silane/oxo-rhenium complexes
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This work reports a novel method for the reduction of sulfoxides with silanes catalyzed by high valent oxo-rhenium(V) and (VII) complexes. The catalytic system PhSiH3/ReIO2(PPh3)2 (1 mol %) proved to be highly efficient for the reduction of a wide range of sulfoxides in excellent yields under mild conditions. This novel methodology is also highly chemoselective, tolerating several functional groups such as -CHO, -CO2R, -Cl, -NO2, and double or triple bonds.
- Sousa, Sara C.A.,Fernandes, Ana C.
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experimental part
p. 6872 - 6876
(2010/05/03)
-
- Facile synthesis of substituted thiophenes via Pd/C-mediated sonogashira coupling in water
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The first successful Pd/C-mediated Sonogashira coupling of iodothiophene with terminal alkynes in water is described here. Pd/C-CuI-PPh3 was found to be an efficient catalyst system for this coupling reaction. Using this economic and reliable process a variety of acetylenic thiophenes with a wide range of functional groups were prepared in good yields. Synthetic applications and in vitro anticancer properties of some of the compounds synthesized are described.
- Raju, Sirisilla,Kumar, P. Rajender,Mukkanti,Annamalai, Pazhanimuthu,Pal, Manojit
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p. 6185 - 6189
(2012/05/07)
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- Stannylated allylsulfones as versatile new building blocks
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Propargylic sulfones undergo regioselective hydrostannation in the presence of Mo(CO)3(CNt-Bu)3(MoBl3), giving rise to stannylated allyl sulfones. These are interesting building blocks, because in the first step the vinyls
- Kazmaier, Uli,Wesquet, Alexander
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p. 1271 - 1274
(2007/10/03)
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- Selective deoxygenation of sulfoxides to sulfides with phosphites catalyzed by dichlorodioxomolybdenum(VI)
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Chemoselective deoxygenation of sulfoxides to sulfides was carried out by P(OPh)3 in mild conditions catalyzed by dichlorodioxomolybdenum(VI).
- Sanz, Roberto,Escribano, Jaime,Aguado, Rafael,Pedrosa, Maria R.,Arnaiz, Francisco J.
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p. 1629 - 1632
(2007/10/03)
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- Intramolecular [4+3] cycloadditions. Towards a synthesis of widdrol
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Certain substituted alkoxyallylic sulfones were alkylated and treated with Lewis acids to produce vinylthionium ions that underwent intramolecular [4+3] cycloaddition reactions with a tethered furan. Manipulation of the cycloadduct led to the synthesis of widdrol. Other attempts to prepare the cycloadducts were made, but none were exceptionally better than the route using vinylthionium ions as intermediates. Interesting aspects of the alkylation chemistry of phenylthio-substituted alkoxyallylic sulfones are detailed as well.
- Harmata, Michael,Kahraman, Mehmet,Adenu, Gilbert,Barnes, Charles L.
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p. 583 - 618
(2007/10/03)
-
- Improved synthesis of 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP)
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A convenient preparation of 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP, 1) is available through the one-pot propargylation and oxidation of thiophenol to give the propargyl sulfone 11, which is isomerized and brominated in another one-pot reaction. The
- VanZanten, Aaron,Mullaugh, Katherine,Harrington, Ryan,Kiefer, Adam,Carlson, David,Mastarone, Dan,Lipchik, Corey,Murphree, S. Shaun
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p. 2611 - 2613
(2007/10/03)
-
- Iron(II)-catalyzed sulfimidation and [2,3]-sigmatropic rearrangement of propargyl sulfides with tert-butoxycarbonyl azide. Access to N-allenylsulfenimides
-
The iron(II)-catalyzed Bach reaction of tert-butoxycarbonyl azide (BocN3) and allyl sulfides has been extended to include propargyl sulfides, which give N-allenylsulfenimide products. Using 10 mol % dppeFeCl2 as catalyst the reaction
- Bacci, James P.,Greenman, Kevin L.,Van Vranken, David L.
-
p. 4955 - 4958
(2007/10/03)
-
- Prototropic rearrangement of 2-propynyl(methyl)amino, 2-propynyloxy, and 2-propynylsulfanyl derivatives of hetarenes under conditions of phase-transfer catalysis: Mechanism and limitations
-
2-Propynyl derivatives of N-methylaniline, phenol, benzenethiol, 2-pyridinethiol, 2-pyrimidinethiol, and 1,3-benzoxazole-2-thiol were synthesized. Under conditions of phase-transfer catalysis, phenyl 2-propynyl sulfide is converted into allenyl phenyl sul
- Rubina,Fleisher,Abele,Popelis,Lukevits
-
p. 963 - 967
(2007/10/03)
-
- A novel 3,4-bis(sulfenyl)- or 4-selenenyl-3-sulfenylpenta-2,4-dienylation of aldehydes using 4-ethoxy-1,2-bis(sulfenyl)- or 1-selenenyl-2-sulfenylbuta-1, 3-dienyl lithiums
-
3,4-Dichalcogenopenta-2,4-dienylation of aldehydes proceeded in good to high yields using 4-ethoxy-1-(benzenesulfenyl)-2-(methanesulfenyl)- (5), 4-ethoxy-1,2-bis(benzenesulfenyl)but-1,3-diene (6), and 1-selenenyl derivatives 7 and 8. This novel four-carbo
- Yoshimatsu, Mitsuhiro,Matsuura, Yasutaka,Gotoh, Kohei
-
p. 1405 - 1412
(2007/10/03)
-
- Highly selective sulfoxidation of allylic and vinylic sulfides by hydrogen peroxide using a flavin as catalyst
-
A highly chemoselective oxidation of allylic and vinylic sulfides to the corresponding sulfoxides has been developed using flavin 1 as the oxidation catalyst and hydrogen peroxide as the terminal oxidant. The sulfoxides were formed in good to excellent yields in a highly selective manner even when an excess of the oxidant was used. Sulfone formation was completely suppressed to 0.5% (in one single case 1.5% sulfone was detected). No epoxidation of double bonds or interference with other functional groups was observed under the reaction conditions. The general applicability was demonstrated by the selective oxidation of various allylic and vinylic sulfides having different electronic properties. A number of functionalities including hydroxy, acetoxy, amino, silyloxy, and formyl groups are tolerated under these mild reaction conditions.
- Linden, Auri A.,Krueger, Lars,Baeckvall, Jan-E.
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p. 5890 - 5896
(2007/10/03)
-
- Amination and [2,3]-sigmatropic rearrangement of propargylic sulfides using a ketomalonate-derived oxaziridine: synthesis of N-allenylsulfenimides.
-
Amination of propargylic sulfides with a ketomalonate-derived oxaziridine under metal free conditions gives N-Boc-N-allenylsulfenimides via [2,3]-sigmatropic rearrangement.
- Armstrong, Alan,Cooke, Richard S,Shanahan, Stephen E
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p. 3142 - 3143
(2007/10/03)
-
- Synthesis and cytotoxicity of 3-(hetarylthio)-1-propynyl-(trimethyl)silanes
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We have developed a two-step method for synthesis of 3-(hetarylthio)-1-propynyl(trimethyl)silanes from thiols in a phase-transfer catalysis system HC≡CCH2Br-solid K2CO3-18-crown-6-toluene followed by reaction with n-BuLi-Me3SiCl in ether or THF. We have observed that 3-[1,3-bis(trimethylsilyl)-2-propynyl] thioindole displays high cytotoxicity in HT-1080 and MG-22A tumor cell lines.
- Abele,Abele,Rubina,Dzenitis,Arsenyan,Shestakova,Nesterova,Domracheva,Popelis,Grinberga,Lukevics
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p. 867 - 872
(2007/10/03)
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- Depropargylation under palladium-copper catalysis: Synthesis of diaryl sulfides
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3-[2-(N-p-Toluenesulfonyl)aminophenylthio]prop-1-yne, reacted with aryl iodides in the presence of Et3N in THF solution with (PPh3)2PdCl2 (3 mol%) and CuI (40 mol%) at room temperature for 8 h followed by reflux
- Kundu, Nitya G,Nandi, Bidisha
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p. 5885 - 5895
(2007/10/03)
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- Stereoselective synthesis of (Z)-α-phenoxymethylene-γ-butyrolactone and its sulfur analogues from 2-propynyloxy- or 2-propynylthiobenzene
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The preparations of (Z)-α-phenoxymethylene-γ-butyrolactone, α-phenoxymethyl-γ-butyrolactone, (Z)-α-phenylthiomethylene-γ-butyrolactone, and α-phenylthiomethyl-γ-butyrolactone derivatives from 2-propynyloxy-benzene and 2-propynylthiobenzene were described.
- Luo, Fen-Tair,Ko, Seng-Li,Liu, Lijun,Chen, Hui
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p. 2055 - 2066
(2007/10/03)
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- 3-Arylthio- and 3-aroxy-1-propynes and their reactions with amines
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3-Arylthio and 3-aroxy-1-propynes can be prepared by reaction of substituted 3-bromo-1-propynes with arylthio- and aroxytrimethylstannanes. Stannylation of 3-arylthio-1-trimethylsilyl-1-propynes with diethyl(trimethylslannyl)amine is accompanied by cleavage of the Si-Csp bond.
- Bogoradovskii,Maksimov,Zubova
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p. 1167 - 1172
(2007/10/03)
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- Synthesis of organic sulfides using Ce-exchanged NaY catalyst
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Synthesis of organic sulfides from thiols and alkyl halides is achieved using Ce-exchanged zeolite catalyst, Ce(72percent)NaY.
- Reddy, T. Indrasena,Varma, Rajender S.
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p. 621 - 622
(2007/10/03)
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- Development of modified Pauson-Khand reactions with ethylene and utilisation in the total synthesis of (+)-taylorione
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Two complementary Pauson-Khanol annulation protocols for use with the gaseous alkene, ethylene, are described. These N-oxide promoted reactions (10 examples) are shown to proceed under both mild autoclave condition or, more conveniently, at atmospheric pressure. The developed methodology has been utilised as the key transformation in the total synthesis of the sesquiterpene (+)-taylorione which has been realised in a good overall yield from readily available (+)-2-carene.
- Donkervoort, Johannes G.,Gordon, Alison R.,Johnstone, Craig,Kerr, William J.,Lange, Udo
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p. 7391 - 7420
(2007/10/03)
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- Tin Radical Addition to Alkynyl Sulfides: Reactivity of the Intermediate Thioalkyl-Substituted β-(Tributylstannyl)vinyl Radicals
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Phenyl and benzyl alkynyl sulfides 1a-g and 3a, phenylalkynylamines 19a,b, ethers 22a,b, and selenide 31 reacted with tributyltin radicals to give intermediate β-stannylvinyl radicals, whose fate depended on the nature of the side chain. 4-Phenylthio-substituted but-1-en-2-yl radicals underwent stereospecific 5-exo cyclization on the adjacent phenyl ring.The resulting spirocyclohexadienyl radicals gave thiophenes and thiopyrans by carbon-sulfur bond scission or ring expansion on the exocyclic double bond, respectively.Similar behavior was exhibited by the corresponding selenium-containing radical, which afforded a selenophene almost exclusively. (Benzylthio)alkyl-substituted radicals gave products deriving from intramolecular SH2 substitution at the sulfur atom, whereas propargyl sulfides yielded a stannylallene via a β-scission reaction.No 6(or more)-membered ring closure was observed with pentynyl and hexynyl phenyl sulfides 1b,c, which gave only the (E)-addition products of tin hydride; oxygen- and nitrogen-containing vinyl radicals also gave the (E)-adducts exclusively.An interaction between the unpaired electron orbital and the empty low-energy orbitals of the heteroatom might explain why sulfur and selenium can undergo 5-exo cyclization.
- Capella, Laura,Montevecchi, Pier Carlo,Nanni, Daniele
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p. 3368 - 3374
(2007/10/02)
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- Preparation of Benzothiophenes by Pd(0)-Catalyzed Intramolecular Cyclization of Allyl (and Propargyl) o-Iodophenyl Sulfides
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Benzothiophenes are prepared by intramolecular Pd(0)-catalyzed Heck reaction of allyl o-iodophenyl sulfides.Pd(0)-Catalyzed intramolecular cyclization of o-iodophenyl propargyl sulfide in the presence of a hydride donor gives 3-methylene-2,3-dihydrobenzothiophene, which reacts with several enophiles in ene type reactions.However, allyl (and propargyl) aryl sulfides react with palladium(II) chloride to afford polymeric 2.
- Arnau, Narcis,Moreno-Manas, Marcial,Pleixats, Roser
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p. 11019 - 11028
(2007/10/02)
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- Stereoselectivity in the sigmatropic rearrangement of eight- and nine-membered cyclic allylsulfonium ylides. Synthesis of vinyl- substituted butyro- and valerolactones
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The rhodium (II) acetate-catalyzed [2,3]sigma-tropic rearrangement of the diazo malonates of (z)-4-phen-ylthio-2-buten-1-ol derivatives 6 afforded vinyl-substituted butyrolactones 10 in a highly stereoselective manner, while the rearrangement of the diazo malonates of homologues, (z)-5-phenylthio-3-penten-1-ol derivatives 9, yielded vinyl-substituted valerolactones 13 and 14 in the predominance of the formers. A stereochemically fixed substituent R in 9 was found to be an important factor resulting to high stereoselectivity in the latter rearrangement as shown by using diazo malonate 20b as substrate.
- Kido, Fusao,Sinha, Subhash C.,Abiko, Toshiya,Watanabe, Masataka,Yoshikoshi, Akira
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p. 4887 - 4906
(2007/10/02)
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- Studies on the Addition of Allyl Oxides to Sulfonylallenes. Preparation of Highly Substituted Allyl Vinyl Ethers for Carbanionic Claisen Rearrangements
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Thirty-five allyl vinyl ethers bearing an arylsulfonyl anion-stabilizing group have been prepared by addition of allylic alkoxides to (arylsulfonyl)allenes.The allyl vinyl ethers are produced as either β,γ-unsaturated or α,β-unsaturated sulfones depending upon the substitution pattern of the allene and the reaction conditions.A wide variety of substitution patterns are available by using this method.Factors that control the position and stereochemistry of the vinyl ether double bond are discussed.
- Denmark, Scott E.,Harmata, Michael A.,White, Kathleen S.
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p. 4031 - 4042
(2007/10/02)
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- Mass Spectral Rearrangements of 3-Arylsulphonyl-2-arylthiopropenes and N-(4'-Arylsulphonyl-2'-butynyl)-N-(4"-arylthio-2"-butynyl)anilines
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Under electron impact the title compounds undergo skeletal rearrangement in the addition to the anticipated modes of cleavage.The 3-arylsulphonyl-2-arylthiopropenes readily eliminate sulphur dioxide.Other modes of fragmentation include rearrangement to a
- Glaspy, P. E.,Hancock, R. A.,Thyagarajan, B. S.
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p. 281 - 287
(2007/10/02)
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