- The energy-transfer-enabled biocompatible disulfide–ene reaction
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Sulfur-containing molecules participate in many essential biological processes. Of utmost importance is the methylthioether moiety, present in the proteinogenic amino acid methionine and installed in tRNA by radical-S-adenosylmethionine methylthiotransferases. Although the thiol–ene reaction for carbon–sulfur bond formation has found widespread applications in materials or medicinal science, a biocompatible chemo- and regioselective hydrothiolation of unactivated alkenes and alkynes remains elusive. Here, we describe the design of a general chemoselective anti-Markovnikov hydroalkyl/aryl thiolation of alkenes and alkynes—also allowing the biologically important hydromethylthiolation—by triplet–triplet energy transfer activation of disulfides. This fast disulfide–ene reaction shows extraordinary functional group tolerance and biocompatibility. Transient absorption spectroscopy was used to study the sensitization process in detail. The hereby gained mechanistic insights were successfully employed for optimization of the catalytic system. This photosensitized transformation should stimulate bioimaging applications and carbon–sulfur bond-forming late-stage functionalization chemistry, especially in the context of metabolic labelling.
- Teders, Michael,Henkel, Christian,Anh?user, Lea,Strieth-Kalthoff, Felix,Gómez-Suárez, Adrián,Kleinmans, Roman,Kahnt, Axel,Rentmeister, Andrea,Guldi, Dirk,Glorius, Frank
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p. 981 - 988
(2018/08/31)
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- Novel atom-economic reaction: Comprehensive utilization of S-alkylisothiouronium salt in the synthesis of thioethers and guanidinium salts
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A novel atom-economic three-component one-pot reaction of a primary amine, an S-alkylisothiouronium salt and a Michael receptor is reported, which affords a guanidinium salt and thioether simultaneously. The guanidine moiety is involved in catalyzing the conjugated Michael addition of the mercaptan. The reaction proceeds under ambient conditions using a non-toxic EtOH-H2O mixture as the solvent, and the two products can be very easily purified. Complete atom economy is achieved by fully utilizing the S-alkylisothiouronium salt and converting the previously wasted mercaptan by-product into the valuable thioether.
- Gao, Pengchao,Leng, Penglin,Sun, Qi,Wang, Xin,Ge, Zemei,Li, Runtao
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p. 17150 - 17155
(2013/09/24)
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- PROCESS FOR THE ADDITION OF THIOLATES TO ?,?-UNSATURATED CARBONYL OR SULFONYL COMPOUNDS
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Alkylthio substituted aldehydes, ketones, esters and sulfones are prepared by reacting α,β-unsaturated carbonyl and sulfonyl compounds with a sodium or potassium thiolate in the presence of a alkane carboxylic acid and water.
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Page/Page column 4-5
(2010/03/31)
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- Pronounced catalytic effect of a micellar solution of sodium dodecyl sulfate (SDS) on the efficient C-S bond formation via an odorless thia-michael addition reaction through the in situ generation of S-alkylisothiouronium salts
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A pronounced catalytic effect of sodium dodecyl sulfate (SDS) was observed on the in situ production of 5-alkylisothiouronium salts via the reaction of primary, allyl and benzyl halides with thiourea in SDS droplets .Hydrolysis of the generated Salkylisot
- Firouzabadi, Habib,Iranpoor, Nasser,Abbasi, Mohammad
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experimental part
p. 755 - 766
(2009/11/30)
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- A facile generation of C-S bonds via one-pot, odourless and efficient thia-Michael addition reactions using alkyl, aryl or allyl halides, thiourea and electron-deficient alkenes in wet polyethylene glycol (PEG 200) under mild reaction conditions
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An efficient and odourless synthesis of thia-Michael adducts by the reaction of various organic halides (primary, secondary, tertiary, allylic, and benzylic), structurally diverse electron-deficient alkenes (ketones, esters, and acrylonitrile) and thioure
- Firouzabadi, Habib,Iranpoor, Nasser,Abbasi, Mohammad
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experimental part
p. 5293 - 5301
(2009/11/30)
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- Thia-Michael addition using cheap and odorless S-alkylisothiouronium salts as thiol equivalents in water
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S-Alkylisothiouronium salt has been found to be a non-toxic, odorless and simply operational alternative of thiol for the thia-Michael addition with electron-deficient olefins. The reactions were carried out under alkaline conditions in water at room temperature within 5-20 minutes to afford the expected products in good to excellent yields. Georg Thieme Verlag Stuttgart.
- Zhao, Yan,Ge, Ze-Mei,Cheng, Tie-Ming,Li, Run-Tao
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p. 1529 - 1532
(2008/02/04)
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- Facile Formation of Lanthanoid(III) Thiolates from Benzophenone-Catalyzed Reaction of Lanthanoid Metals and Disulfides, and Their Use as Sulfenylating Reagents
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Lanthanoid metal reacts with diaryl and -alkyl disulfides in the presence of a catalytic amount of benzophenone to generate lanthanoid(III) thiolates.Lanthanoid thiolates thus formed in situ, react with enones to give Michael adducts in good yields.
- Taniguchi, Yuki,Maruo, Masafumi,Takaki, Ken,Fujiwara, Yuzo
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p. 7789 - 7792
(2007/10/02)
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- DIMETHYLALUMINIUM METHANESELENOLATE - A USEFUL REAGENT FOR THE PREPARATION OF SELENOESTERS. A NEW FRIEDEL-CRAFTS ACYLATION PROCEDURE PROMOTED BY Cu(I)
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The preparation of a new aluminium reagent, dimethylaluminium methaneselenolate (Me2AlSeMe) is described.The reactivity of this aluminium reagent toward a variety of organic substrates has been studied.Me2AlSeMe will convert O-alkyl esters to selenoesters in high yield.These selenoesters function as extremely reactive acyl transfer agents and are converted to acids, esters, and amides on reaction with water, alcohols or amines in the presence of a selenophilic metal cation.The selenoesters will, moreover, acylate reactive arenes and heterocyclic compounds when cuprous triflate is employed as the selenophilic metal cation.This latter transformation constitutes a new transition metal promoted variant of the Friedel-Crafts acylation reaction.
- Kozikowski, Alan P.,Ames, Anthony
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p. 4821 - 4834
(2007/10/02)
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