- Solvent-mediated switching between oxidative addition and addition-oxidation: Access to β-hydroxysulfides and β-arylsulfones by the addition of thiols to olefins in the presence of Oxone
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The reaction between aryl olefins and thiols in the presence of Oxone in toluene-water (9:1, v/v) affords β-hydroxy-2-arylethyl aryl sulfides smoothly by the interception of intermediary thiyl radicals with aryl olefins; the former are generated by the ox
- Moorthy, Jarugu Narasimha,Payra, Soumen,Yadav, Navin
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p. 582 - 591
(2022/01/22)
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- Base-Mediated Radical Borylation of Alkyl Sulfones
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A practical and direct method was developed for the production of versatile alkyl boronate esters via transition metal-free borylation of primary and secondary alkyl sulfones. The key to the success of the strategy is the use of bis(neopentyl glycolato) diboron (B2neop2), with a stoichiometric amount of base as a promoter. The practicality and industrial potential of this protocol are highlighted by its wide functional group tolerance, the late-stage modification of complex compounds, no need for further transesterification, and operational simplicity. Radical clock, radical trap experiments, and EPR studies were conducted which show that the borylation process involves radical intermediates.
- Huang, Mingming,Hu, Jiefeng,Krummenacher, Ivo,Friedrich, Alexandra,Braunschweig, Holger,Westcott, Stephen A.,Radius, Udo,Marder, Todd B.
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supporting information
(2021/12/02)
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- Visible- And UV-Light-Induced Decarboxylative Radical Reactions of Benzoic Acids Using Organic Photoredox Catalysts
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Photoinduced decarboxylative radical reactions of benzoic acids with electron-deficient alkenes, diborane, and acetonitrile under organic photoredox catalysis conditions and mild heating afforded adducts, arylboronate esters, and the reduction product, respectively. The reaction is thought to involve single-electron transfer promoted the generation of aryl radicals via decarboxylation. A diverse range of benzoic acids were found to be suitable substrates for this photoreaction. Only our two-molecule organic photoredox system can work well for the direct photoinduced decarboxylation of benzoic acids.
- Kubosaki, Suzuka,Takeuchi, Haruka,Iwata, Yutaka,Tanaka, Yosuke,Osaka, Kazuyuki,Yamawaki, Mugen,Morita, Toshio,Yoshimi, Yasuharu
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p. 5362 - 5369
(2020/05/19)
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- A Study of Graphene-Based Copper Catalysts: Copper(I) Nanoplatelets for Batch and Continuous-Flow Applications
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The use of graphene derivatives as supports improves the properties of heterogeneous catalysts, with graphene oxide (GO) being the most frequently employed. To explore greener possibilities as well as to get some insights into the role of the different gr
- De Angelis, Sonia,Franco, Mario,Triminì, Alessandra,González, Ana,Sainz, Raquel,Degennaro, Leonardo,Romanazzi, Giuseppe,Carlucci, Claudia,Petrelli, Valentina,de la Esperanza, Alejandro,Go?i, Asier,Ferritto, Rafael,Ace?a, José Luis,Luisi, Renzo,Cid, M. Belén
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supporting information
p. 3011 - 3018
(2019/08/20)
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- Green Organocatalytic Oxidation of Sulfides to Sulfoxides and Sulfones
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A highly efficient synthetic methodology towards the selective synthesis of sulfoxides and sulfones is reported using a cheap and green organocatalytic method. Starting from sulfides and using 2,2,2-trifluoroacetophenone as the organocatalyst and H2O2 as the oxidant, the high-yielding preparation of sulfoxides or sulfones is described, being dependent on the reaction conditions.
- Voutyritsa, Errika,Triandafillidi, Ierasia,Kokotos, Christoforos G.
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p. 917 - 924
(2017/02/15)
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- Acid-Catalyzed Oxidative Addition of Thiols to Olefins and Alkynes for a One-Pot Entry to Sulfoxides
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An oxidative variant of the thiol-ene reaction has been developed, achieving the direct addition of thiols to olefins to form sulfoxides. The reaction uses tert-butyl hydroperoxide as oxidant and methanesulfonic acid as catalyst. The latter is believed to catalyze the oxidation of the intermediate sulfide to the sulfoxide. No special precautions are necessary to exclude oxygen, yet the products are formed without oxidation at the β-position. Styrenes, acrylic acid derivatives, alkynes, and thiophenols gave the highest yields, while aliphatic olefins and thiols were less effective.
- Yue, Hui-Lan,Klussmann, Martin
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supporting information
p. 2505 - 2509
(2016/10/24)
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- Nickel-catalyzed α-benzylation of sulfones with esters: Via C-O activation
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The nickel-catalyzed α-benzylation of sulfones with readily available benzylic alcohol derivatives was achieved via C-O activation. The transformation was complete in 30 minutes using a simple Ni(COD)2 as a catalyst without any additional ligan
- Xiao, Jing,Yang, Jia,Chen, Tieqiao,Han, Li-Biao
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p. 42656 - 42659
(2016/05/19)
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- Synthesis of arylethyl (E)-styrylsulfones and arylsulfones by one-pot DIBAL-H/NaH-mediated reaction of β-ketosulfones
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A facile one-pot synthetic route for preparing a series of arylethyl (E)-styrylsulfones or arylethyl arylsulfones is developed. The efficient one-pot DIBAL-H/NaH-mediated route includes reduction of α-benzyl-β- arylketosulfones and retroaldol/aldol or retro aldol reaction of the resulting intermediate. The DIBAL-H/NaH-mediated reaction mechanism has been discussed. Georg Thieme Verlag Stuttgart. New York.
- Chang, Meng-Yang,Chen, Yi-Chia,Chan, Chieh-Kai
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p. 1739 - 1744
(2014/08/05)
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- Tuning the lewis acidity of boranes in frustrated lewis pair chemistry: Implications for the hydrogenation of electron-poor alkenes
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An analysis of the metal-free reduction of electron deficient olefins by frustrated Lewis pairs indicates that the rate-determining step might be either the heterolytic cleavage of H2 to form an -onium borohydride salt, or the subsequent transfer of the hydride moiety to the substrate following a Michael-type addition reaction. While the use of strong Lewis acids such as B(C6F5)3 facilitates the first of these processes, hydride transfer to the olefin should be contrarily favoured by the use of weak Lewis acids which, for this very same reason, might be unable to promote the prior H2 split. After systematic testing of several boranes of different Lewis acidity (assessed by using the Childs' method) and steric demand, an optimal situation that employs tris(2,4,6-trifluorophenyl) borane was reached. Mixtures of this borane with 1,4-diazabicyclo[2.2.2]octane (DABCO) exhibited excellent catalytic activity for the hydrogenation of alkylidene malonates. In fact, this transformation could be achieved under milder conditions than those we reported previously. Moreover, the reaction scope could be expanded to other electron deficient olefins containing esters, sulfones or nitro functionalities as electron-withdrawing substituents.
- Nicasio, Juan A.,Steinberg, Sebastian,Ines, Blanca,Alcarazo, Manuel
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p. 11016 - 11020
(2013/09/02)
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- An investigation into the one-pot Heck olefination-hydrogenation reaction
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Herein is described an operationally simple process concerning the observation that, following either inter-, or intramolecular Heck olefination, stirring of the so formed substituted alkenyl product under an atmosphere of hydrogen efficiently effects alkene hydrogenation. Overall this two-operation, one-pot "reductive Heck" sequence is notable since direct reductive Heck processes, using additives such as formate salts, are restricted to a limited range of substrates. In total 25 examples are reported (yields ranging from 0 to 95%), which were selected in order to probe the scope and limitations of this method. Finally, the utility of this sequence was demonstrated in a short synthesis of the calcimimetic agent, cinacalcet.
- Geoghegan, Kimberly,Kelleher, Susan,Evans, Paul
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experimental part
p. 2187 - 2194
(2011/05/14)
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- THIOREDOXIN AND THIOREDOXIN REDUCTASE INHIBITORS
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The present invention relates to sulfone derivatives and to their use as modulators of the thioredoxin/thioredoxin reductase redox system, including for the treatment and/or prevention of pathophysiological conditions mediated by thioredoxin/thioredoxin reductase, such as cancer, HIV/ AIDS, Alzheimer's disease, rheumatoid arthritis, and skin disorders. Also provided are pharmaceutical compositions comprising the inventive sulfones.
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Page/Page column 58; 13/22; 14/22
(2008/06/13)
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- Alkene synthesis: Elimination of arenesulfinic acid from alkyl aryl sulfones using potassium trimethylsilanolate as base
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The use of potassium trimethylsilanolate as base to induce elimination of potassium arenesulfinate from alkyl aryl sulfones to produce E-alkenes is described. The reaction was appropriate for substrates containing a benzyl or allyl group α to the sulfone
- Baker-Glenn, Charles A.G.,Barrett, Anthony G.M.,Gray, Andrew A.,Procopiou, Panayiotis A.,Ruston, Mark
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p. 7427 - 7430
(2007/10/03)
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- Preparation of alcohols from sulfones and trialkylboranes
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The reaction of sulfone anions with trialkylboranes followed by thermal isomerization of the obtained boron compounds in the presence of excess borane-methyl sulfide complex and by alkaline hydroperoxide oxidation yields primary alcohols.
- Billaud, Célia,Goddard, Jean-Philippe,Le Gall, Thierry,Mioskowski, Charles
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p. 4451 - 4454
(2007/10/03)
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- Mechanistic organic chemistry in a microreactor. Zeolite-controlled photooxidations of organic sulfides
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The intrazeolite and solution photooxygenations of a series of sulfides have been compared. The unusual zeolite environment enhances the rates of reaction, it suppresses the Pummerer rearrangements, and it has a dramatic effect on the sulfoxide/sulfone ratio. A detailed kinetic study utilizing trapping experiments and intramolecular competition provides evidence for cation complexation to a persulfoxide intermediate as the underlying phenomenon for the unique intrazeolite behavior. For example, the enhanced rate of reaction is traced to the cation stabilization of the persulfoxide toward unproductive decomposition to substrate and triplet oxygen.
- Clennan, Edward L.,Zhou, Wenhui,Chan, Jacqueline
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p. 9368 - 9378
(2007/10/03)
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- Oxidative addition of thiols to substituted olefins in the presence of transition metal peroxo complexes under phase-transfer catalysis conditions
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Oxidative addition of thiophenol and isobutanethiol to substituted olefins in the presence of molybdenum, tungsten, and vanadium peroxo complexes under phase-transfer catalysis conditions was shown to give sulfones, the oxidation products of sulfides formed in the first step, and disulfides as the oxidation products of thiols. The product ratio of the reaction depends on the structure of an olefin, thiol, and the peroxo complex used. Copyright 1999 by MAHK "Hayka/Interperiodica" (Russia).
- Zhirukhina,Thanaa, Al-Haddad,Tarakanova,Litvinova,Kulikov,Anisimov
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p. 105 - 107
(2007/10/03)
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- Integrated Chemical Process: One-Pot Double Elimination Method for Acetylenes
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A novel one-pot process for synthesis of acetylenes has been achieved in which the following series of steps are integrated: addition of an α-anion of sulfone to aldehyde; trapping of the resulting adduct to incorporate a leaving group, and double elimination of this intermediate. Consolidation of Peterson elimination renders the process much simpler. This method provides a convenient and high-yielding access to a variety of enynes and polyynes as well as to functionally substituted aryl acetylenes containing halogen(s) or acetal groups, which are useful building blocks for aryl acetylene scaffolds. Iteration of the one-pot generation of acetylenic bonds provides a new metodology for the buildup of aryl acetylene skeletons.
- Orita, Akihiro,Yoshioka, Naonori,Struwe, Petra,Braier, Arnold,Beckmann, Anke,Otera, Junzo
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p. 1355 - 1363
(2007/10/03)
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