- Synthetic Studies on the Preparation of Alanyl Epoxysulfones as Cathepsin Cysteine Protease Electrophilic Traps
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A Darzens reaction between tert-butoxycarbonyl alaninal and chloromethyl phenyl sulfone afforded chlorohydrins, which were converted into epoxysulfones by reaction with sodium tert-butoxide. Epoxysulfone 10 and chloroketone 14 derived from chlorohydrins by oxidation proved to be inhibitors of cathepsins H, S, and C as determined by competitive activity-based protein profiling.
- Latorre, Antonio,Rodríguez, Santiago,González, Florenci V.,Florea, Bogdan I.,Overkleeft, Herman S.
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Read Online
- Ni-Catalyzed Asymmetric Reductive Alkenylation of α-Chlorosulfones with Vinyl Bromides
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A nickel-catalyzed enantioconvergent reductive cross-coupling of α-chlorosulfones with vinyl bromides is described here. This strategy enables the enantioselective construction of chiral allylic sulfones from simple α-chlorosulfones and vinyl bromides. The mild reaction conditions lead to excellent functional group compatibility, as evidenced by the broad substrate scope and tolerance of complex bioactive molecules. Our preliminary mechanistic study suggests that this enantioselective vinylation process operates through a radical intermediate.
- Geng, Jingjing,Song, Yanhong,Sun, Deli,Tong, Weiqi,Wu, Fan
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supporting information
p. 1807 - 1811
(2022/03/27)
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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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- Controlled α-mono- and α,α-di-halogenation of alkyl sulfones using reagent-solvent halogen bonding
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The direct and selective α-mono-bromination of alkyl sulfones was achieved through base-mediated electrophilic halogenation. The appropriate combination of solvent and electrophilic bromine source was found to be critical to control the nature of the products formed, where reagent-solvent halogen bonding is proposed to control the selectivity via alteration of the effective size of the electrophilic bromine source. Conversely, the α,α-di-brominated sulfones were selectively obtained in good yields following polyhalogenation followed by selective de-halogenation during workup. Both procedures can be applied on gram scale, and the mono-halogenation was successfully extended to the fully selective α-chlorination, α-iodination and α-fluorination of alkyl sulfones.
- Poteat, Christopher M.,Lindsay, Vincent N. G.
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supporting information
p. 2912 - 2915
(2019/03/17)
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- 2,4-Disubstituted 5-Nitroimidazoles Potent against Clostridium difficile
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Metronidazole is one of the first-line treatments for non-severe Clostridium difficile infections (CDI). However, resistance limits its use in cases of severe and complicated CDI. Structure–activity relationships previously described for the 5-nitroimidazole series have shown that functionalization at the 2- and 4-positions can impart better activity against parasites and anaerobic bacteria than metronidazole. Herein we report the synthesis of new 2,4-disubstituted 5-nitroimidazole compounds that show potent antibacterial activity against C. difficile. We used a vicarious nucleophilic substitution of hydrogen (VNS) reaction to introduce a phenylmethylsulfone at the 4-position and a unimolecular radical nucleophilic substitution (SRN1) reaction to introduce an ethylenic function at the 2-position of the 5-nitroimidazole scaffold.
- Spitz, Cédric,Mathias, Fanny,Péchiné, Séverine,Doan, Tri Hanh Dung,Innocent, Jean,Pellissier, Sylvain,Di Giorgio, Carole,Crozet, Maxime D.,Janoir, Claire,Vanelle, Patrice
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p. 561 - 569
(2019/02/13)
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- Sulfone compound (by machine translation)
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[Problem] to safely and conveniently, highly selective, sulfide compound producing a sulfone compound. [Solution] pH is 9 - 12 under, water or water-insoluble solvent or an aromatic hydrocarbon-based solvent mixture, sodium hypochlorite is used as oxidizing agent, (1) (2) from the compound represented by the formula sulfide sulfone compound represented by the formula manufacturing method. (R1 And R2 Are each independently an alkyl, aryl, aralkyl, heteroaryl)[Drawing] no (by machine translation)
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Paragraph 0046
(2017/10/06)
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- Lowering of 5-nitroimidazole's mutagenicity: Towards optimal antiparasitic pharmacophore
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To improve the antiparasitic pharmacophore, 20 5-nitroimidazoles bearing an arylsulfonylmethyl group were prepared from commercial imidazoles. The antiparasitic activity of these molecules was assessed against Trichomonas vaginalis, the in vitro cytotoxicity was evaluated on human monocytes and the mutagenicity was determined by the Salmonella mutagenicity assay. All IC50 on T. vaginalis were below the one of metronidazole. The determination of the specificity indexes (SIs), defined as the ratios of the cytotoxic activity and the antitrichomonas activity, indicated that 11 derivatives had a SI over the one of metronidazole. Molecules, bearing an additional methyl group on the 2-position, showed a lower mutagenicity than metronidazole. Moreover, three derivatives were characterized by a low mutagenicity and an efficient antitrichomonas activity.
- Crozet, Maxime D.,Botta, Celine,Gasquet, Monique,Curti, Christophe,Remusat, Vincent,Hutter, Sebastien,Chapelle, Olivier,Azas, Nadine,De Meo, Michel,Vanelle, Patrice
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scheme or table
p. 653 - 659
(2009/09/08)
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- AMINOAZACYCLYL-3-SULFONYLINDAZOLES AS 5-HYDROXYTRYPTAMINE-6 LIGANDS
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The present invention provides a compound of formula I and the use thereof in the therapeutic treatment of disorders related to or affected by the 5-HT6 receptor.
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Page/Page column 12
(2009/01/20)
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- Chemoselective mono halogenation of β-keto-sulfones using potassium halide and hydrogen peroxide; synthesis of halomethyl sulfones and dihalomethyl sulfones
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The synthesis of α-halo β-keto-sulfones using potassium halide and hydrogen peroxide as a chemoselective mono halogenation reagent and the synthesis of α,α-symmetrical and asymmetrical dihalo β-keto-sulfones and α-halo, α-alkyl and β-keto-sulfones is described. Base induced cleavage of α-halo β-keto-sulfones, α,α-dihalo β-keto-sulfones, and α-halo, α-alkyl β-keto-sulfones afforded the corresponding halomethyl sulfones, dihalomethyl sulfones and haloalkyl sulfones.
- Suryakiran,Prabhakar,Srikanth Reddy,Chinni Mahesh,Rajesh,Venkateswarlu
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p. 877 - 881
(2007/10/03)
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- Nucleophilic fluoroalkylation of epoxides with fluorinated sulfones
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The unprecedented nucleophilic fluoroalkylation of simple epoxides with fluorinated sulfones was achieved to give the β-fluoroalkyl alcohols in one step. The negative "fluorine effect" in the nucleophilic fluoroalkylation of epoxides with fluorinated carbanions was probed by the reactivity comparison between carbanions PhSO2CF2 - (3) and PhSO2CCl2- (4) and between carbanions PhSO2CHF- (7) and PhSO2CHCl - (13). The mediation of this fluorine effect by introducing another electron-withdrawing benzenesulfonyl group was found to be an effective way to significantly increase the nucleophilicity of the fluorinated carbanions, with the reactivity order [(PhSO2)2CF-] (16) > PhSO2CFH- (7) ? PhSO2CF2 - (3).
- Ni, Chuanfa,Li, Ya,Hu, Jinbo
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p. 6829 - 6833
(2007/10/03)
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- Rapid synthesis of new 5-nitroimidazoles as potential antibacterial drugs via VNS procedure
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Original 4-arylsulfonylmethyl-5-nitroimidazoles were prepared by reacting four chloromethylaryl sulfones with 5-nitroimidazole derivatives via a vicarious nucleophilic substitution (VNS) of hydrogen reaction. Copyright Taylor & Francis Group, LLC.
- Crozet, Maxime D.,Remusat, Vincent,Curti, Christophe,Vanelle, Patrice
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p. 3639 - 3646
(2007/10/03)
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- [3-(1H-Imidazol-4-yl)propyl]guanidines containing furoxan moieties: A new class of H3-antagonists endowed with NO-donor properties
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Synthesis and pharmacological characterisation of a series of products obtained by coupling the H3-antagonist SKF 91486 through appropriate spacers with the NO-donor 3-phenylfuroxan-4-yloxy and 3-benzenesulfonylfuroxan-4-yloxy moieties, as well as with the corresponding furazan substructures, devoid of NO-donating properties, are reported. All the products were tested for their H3-antagonistic and H2-agonistic properties on electrically-stimulated guinea-pig ileum segments and guinea-pig papillary muscle, respectively. The whole series of compounds displayed good H3-antagonist behaviour and feeble partial H2-agonist activity. Among furoxan derivatives, the benzenesulfonyl hybrid 28, a good NO-donor, triggered a dual NO-dependent muscle relaxation and H3-antagonistic effect on guinea-pig intestine.
- Bertinaria, Massimo,Di Stilo, Antonella,Tosco, Paolo,Sorba, Giovanni,Poli, Enzo,Pozzoli, Cristina,Coruzzi, Gabriella,Fruttero, Roberta,Gasco, Alberto
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p. 1197 - 1205
(2007/10/03)
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- Binuclear manganese complexes as catalysts in the selective and efficient oxidation of sulfides to sulfones
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The binuclear Mn(IV)-Mn(IV) manganese complex 1 catalyzes the periodic acid oxidation of sulfides to sulfones under mild conditions. The reaction was found to be highly selective giving almost quantitative yields of the sulfones even in the presence other easily oxidized groups. Only amines were found to hinder the reaction.
- Barton, Derek H. R.,Li, Wenge,Smith, Jason A.
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p. 7055 - 7058
(2007/10/03)
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- A simple reduction of α-bromosulfones by cat.(PhSe)2/NaBH4
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Reduction of α-bromosulfones 1, 5, 13-16 by cat.(PhSe)2/NaBH4 occurred site-selectively in high yields. This reduction of 1,3- or 1,4-dibromobis(sulfone) 21 and 25 was applied to intramolecular coupling reactions to give the three- and four-membered carbocycles 26-28.
- Yoshimatsu, Mitsuhiro,Ohara, Megumi
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p. 5651 - 5654
(2007/10/03)
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- Selective synthesis of sulfoxides and sulfones by methyltrioxorhenium-catalyzed oxidation of sulfides with hydrogen peroxide
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Methyltrioxorhenium-catalyzed oxidation of sulfides with hydrogen peroxide in ethanol has been found to be an efficient catalytic system for the selective formation of sulfoxides and sulfones. The oxidation using an equimolar amount of hydrogen peroxide afforded sulfoxides in excellent yield, and the use of two molar amounts of hydrogen peroxide gave sulfones quantitatively. Strongly deactivated sulfide, bis(4-nitrophenyl) sulfide, was converted smoothly to the corresponding sulfoxide and sulfone in excellent yields. The functional group in the side chain of sulfide such as a carbon-carbon double bond was not affected under the reaction conditions, and the sulfur atom was selectively oxidized.
- Yamazaki, Shigekazu
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p. 2955 - 2959
(2007/10/03)
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- α-Fluorination of methyl phenyl sulfoxide and related compounds by molecular fluorine: A novel method for the introduction of fluorine into sulfoxides bearing α-H atoms
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Direct formation of α-fluorosulfones from sulfoxides bearing α-H atoms merely by reaction with molecular fluorine (5% F2/N2) is reported, and a novel non-Pummerer-type mechanism is proposed for this α-fluorination reaction.
- Toyota, Akemi,Ono, Yoshinori,Chiba, Jun,Sugihara, Takumichi,Kaneko, Chikara
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p. 703 - 708
(2007/10/03)
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- α-Fluorination of Sulfoxides Bearing α-Hydrogens by Molecular Fluorine. A Novel Method for the Synthesis of α-Fluorosulfones
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Direct formation of α-fluorosulfones from sulfoxides bearing α-hydrogens merely by reacting molecular fluorine (5percent F2/N2) is reported and a possible mechanism for this novel α-fluorination reaction is proposed.
- Chiba, Jun,Sugihara, Takumichi,Kaneko, Chikara
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p. 581 - 582
(2007/10/03)
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- Mild and Selective Oxygenation of Sulfides to Sulfoxides and Sulfones by Perfluoro-cis-2,3-dialkyloxaziridines
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Sulfides are oxidized to sulfoxides by stoichiometric amounts of perfluoro-cis-2,3-dialkyloxaziridines 2.The reactions proceed at -40 deg C with nearly complete selectivity and very good yields.Sulfoxides are also oxidized easily by 2 under mild conditions to corresponding sulfones.The oxidation of some bioactive sulfides (promazine, albendazole, biotin, and others) is also reported.
- DesMarteau, Darryl D.,Petrov, Viacheslav A.,Montanari, Vittorio,Pregnolato, Massimo,Resnati, Giuseppe
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p. 2762 - 2765
(2007/10/02)
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- Organic syntheses with sulfones No. XLII. Oxidation of α-sulfonyl carbanions with cupric salts.
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α-Lithiated phenylalkyl sulfones, on treatment with various cupric salts, give comparable amounts of the α,α'-dimer and the corresponding vinylic sulfone.With cupric acetate or propionate, dehydrogenation occurs selectively: primary sulfones are converted into α,β-unsaturated sulfones in high yield.
- Baudin, Jean-Bernard,Julia, Marc,Rolando, Christian,Verpeaux, Jean-Noael
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p. 493 - 497
(2007/10/02)
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- Organic Syntheses without Solvent: Preparation of Sulfones and Dithioacetals
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Sulfones are prepared by alkylation of sulfinate salts under solid-liquid phase-transfer catalysis without solvent; dithioacetals are obtained by heterogeneous uncatalyzed reactions of potassium arenethiolates and gem-dihaloalkanes.In both cases, the yields are high and the reaction conditions are mild.Some limitations are given.
- Bram, Georges,Loupy, Andre,Roux-Schmitt, Marie Claude,Sansoulet, Jean,Strzalko, Tekla,Seyden-Penne, Jacqueline
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- Vicarious Nucleophilic Substitution of Hydrogen in Nitroarenes with Carbanions of α-Haloalkyl Phenyl Sulfones
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Carbanions of α-chloroalkyl phenyl sulfones and N,N-dialkyl-α-chloroalkanesulfonamides react with nitrobenzenes to effect direct nucleophilic replacement of hydrogen ortho and para to the nitro group, with vicarious loss of chloride anion, to give the corresponding nitrobenzylsulfonyl derivatives.The reaction occurs much more rapidly than the replacement of such good leaving groups as halogen, methoxy, and phenoxy.Most substituents in the nitrobenzene ring do not interfere with the reaction.The effect of substituents in the nitrobenzene and the carbanion on the orientation of the substitution is discussed.
- Makosza, Mieczyslaw,Golinski, Jerzy,Baran, Janusz
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p. 1488 - 1494
(2007/10/02)
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