- Facile One-Pot Access to α-Diazo-β-ketosulfones from Sulfonyl Chlorides and α-Haloketones
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A convenient one-pot approach to the preparation of α-diazo-β-ketosulfones from sulfonyl chlorides is described. It involves the conversion of the sulfonyl chloride to sodium sulfinate, alkylation of the latter with α-haloketones followed by diazo transfer using the 'sulfonyl-azide-free' ('SAFE') protocol in aqueous medium. The simple and expedient method relies on readily available starting materials and provides facile access to a wide variety of valuable diazo reagents for organic synthesis.
- Dar'In, Dmitry,Kantin, Grigory,Bakulina, Olga,Krasavin, Mikhail
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p. 2259 - 2266
(2020/08/26)
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- Method for synthesizing beta-carbonyl sulfone compound
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The invention discloses a method for synthesizing a beta-carbonyl sulfone compound. The method comprises the steps that sulfinate and a carbonyl compound containing alpha-position active hydrogen areused as raw materials, in a solvent, under the oxidation of alkali, sodium iodide, nanomicelle and 1,2-dibromoethane, the reaction is carried out at 60-80 DEG C for 10-12 hours, separation and purification are performed, and the beta-carbonyl sulfone compound is obtained. The method is simple in synthesis process, convenient in operation, mild in reaction condition, low in cost and high in yield,does not use transition metal catalysis, and is green and safe.
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Paragraph 0016; 0017
(2019/06/13)
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- Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Br?nsted acids. NMR and DFT study of these cations and their reactions
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In strong Br?nsted acids (CF3SO3H, FSO3H, D2SO4), (arysulfonyl)allenes (ArSO2-CR1=C=CR2R3) and (arylsulfinyl)allenes (ArSO-CR1=C=CR2R3) undergo cyclization into the corresponding stable 1,2-oxathiolium ions, which were studied by means of NMR and DFT calculations. Quenching of solutions of these cations with low nucleophilic media, aqueous HCl, leads to their deprotonation with a stereoselective formation of (arysulfonyl)butadienes (for instance, ArSO2-CR1=C-C(Me)=CH2, for R2 = R3 = Me, yields of 87-98%). Reactions of (arysulfonyl)allenes in the system TfOH (0.1 equiv)-HFIP (hexafluoropropan-2-ol) followed by hydrolysis give rise to allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3, yields of 78-99%). Reflux of solutions of (arysulfonyl)allenes in the presence of TfOH (1 equiv) in 1,2-dichlorobenzene leads to the cyclization into thiochromene 1,1-diox-ides in high yields. Under the action of TfOH or AlX3 (X = Cl, Br) followed by hydrolysis of reaction mixtures, (arylsulfinyl)allenes give allyl alcohols (ArSO2-CR1=CH-C(OH)R2R3). Plausible reaction mechanisms have been proposed for all studied reactions.
- Lozovskiy, Stanislav V.,Ivanov, Alexander Yu.,Khoroshilova, Olesya V.,Vasilyev, Aleksander V.
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p. 2897 - 2906
(2018/12/13)
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- PQS-enabled visible-light iridium photoredox catalysis in water at room temperature
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An amphoteric PQS-attached photocatalyst has been prepared that undergoes self-aggregation in water into nanomicelles. This covalently bound species enables Ir-based photoredox catalysis to be conducted in the absence of additives or co-solvents. Representative reactions are described using this new catalytic system, which require no additional investment of external energy in the form of heating or cooling. The entire aqueous reaction mixture readily undergoes in-flask recycling and thus, represents a sustainable precious metal technology.
- Bu, Mei-Jie,Cai, Chun,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 1233 - 1237
(2018/03/26)
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- Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C?S Bond Cleavage: Reaction Development and Mechanism Study
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A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C?S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated CuII intermediate, O?O bond homolysis induced C?S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C?S bond cleavage and transformations.
- Du, Bingnan,Wang, Wenmin,Wang, Yang,Qi, Zhenghang,Tian, Jiaqi,Zhou, Jie,Wang, Xiaochen,Han, Jianlin,Ma, Jing,Pan, Yi
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supporting information
p. 404 - 408
(2018/02/21)
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- O -Iodoxybenzoic Acid (IBX)-Iodine Mediated One-Pot Deacylative Sulfonylation of 1,3-Dicarbonyl Compounds: A Synthesis of β-Carbonyl Sulfones
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A combination of o-iodoxybenzoic acid (IBX) and a catalytic amount of iodine is found to promote a facile one-pot deacylative sulfonylation reaction of 1,3-dicarbonyl compounds with sodium sulfinates to yield β-carbonyl sulfones. The present method provides the target products bearing a wide variety of functional groups in one step and in good yields.
- Katrun, Praewpan,Songsichan, Teerawat,Soorukram, Darunee,Pohmakotr, Manat,Reutrakul, Vichai,Kuhakarn, Chutima
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supporting information
p. 1109 - 1121
(2017/02/24)
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- An efficient electrochemical synthesis of β-keto sulfones from sulfinates and 1,3-dicarbonyl compounds
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An efficient electrochemical synthesis of β-keto sulfones from sulfinates and 1,3-dicarbonyl compounds has been developed. The present electrochemical route could afford the target products in high to excellent yields under mild conditions.
- Pan, Xiao-Jun,Gao, Jian,Yuan, Gao-Qing
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p. 5525 - 5530
(2015/08/03)
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- Chemoselective one-pot synthesis of β-keto sulfones from ketones
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A practical method to synthesize substituted β-keto sulfones directly from ketones at room temperature has been developed. This method involves the nucleophilic addition of a base generated enolate to sulfonyl iodide. The reaction shows high chemoselectivity for the addition of a sulfonyl group to an α-carbon over a hydroxyl group. In addition, the given protocol provides good to excellent yields of β-keto sulfones under mild reaction conditions. Moreover, the regiochemical aspect of the protocol is also explored.
- Rawat, Vikas S.,Reddy, Perla L. M.,Sreedhar, Bojja
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p. 5165 - 5168
(2014/01/23)
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- METHOD FOR PRODUCING PYRIDAZINONE COMPOUNDS AND INTERMEDIATE THEREOF
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The present invention relates to a novel method for producing a pyridazinone compound and an intermediate thereof as shown in the following scheme: wherein the symbols are as defined in the specification.
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Page/Page column 307
(2012/03/27)
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- (Arylsulfonyl)acetones and -acetonitriles: New activated methylenic building blocks for synthesis of 1,2,3-triazoles
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β-Keto sulfones and b-nitrile sulfones were used as building blocks for 1,2,3-triazole synthesis in the Dimroth cyclization. It was shown, that sulfone reagents undergo base-catalyzed cyclization under mild conditions (at room temperature) to give 1,2,3-triazoles in moderate to excellent yields. This fact has confirmed the high nucleophilicity of sulfonylmethylenic compounds and allows new synthetic applications. Georg Thieme Verlag Stuttgart.
- Pokhodylo, Nazariy T.,Matiychuk, Vasyl S.,Obushak, Mykola D.
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scheme or table
p. 2321 - 2323
(2010/02/16)
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- Facile polyethylene glycol (PEG-400) promoted synthesis of β-ketosulfones
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An efficient and convenient synthesis of β-ketosulfones is described. Reaction of an α-haloketone with sodium alkyl/aryl sulphinate yields the corresponding β-ketosulfone promoted by polyethylene glycol (PEG-400) as an efficient reaction medium.
- Suryakiran,Reddy, T. Srikanth,Ashalatha,Lakshman,Venkateswarlu
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p. 3853 - 3856
(2007/10/03)
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- A facile one-pot synthesis of β-keto sulfones from ketones under solvent-free conditions
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An easy solvent-free method is described for the conversion of ketones into β-keto sulfones in high yields that involves the in situ generation of α-tosyloxyketones, followed by nucleophilic substitution with sodium arene sulfinate in the presence of tetra-butylammonium bromide at room temperature. The salient features of this one-pot protocol are short reaction times, cleaner reaction profiles, and simple work-up that precludes the use of toxic solvents.
- Kumar, Dalip,Sundaree, Swapna,Rao,Varma, Rajender S.
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p. 4197 - 4199
(2007/10/03)
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- PYRIDINE COMPOUNDS AS INHIBITORS OF DIPEPTIDYL PEPTIDASE IV
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A compound represented by the formula wherein R1 and R2 are the same or different and each is an optionally substituted hydrocarbon group or an optionally substituted hydroxy group; R3 is an optionally substituted aromatic group; R4 is an optionally substituted amino group; L is a divalent chain hydrocarbon group; Q is a bond or a divalent chain hydrocarbon group; and X is a hydrogen atom, a cyano group, a nitro group, an acyl group, a substituted hydroxy group, an optionally substituted thiol group, an optionally substituted amino group or an optionally substituted cyclic group; provided that when X is an ethoxycarbonyl group, then Q is a divalent chain hydrocarbon group. The compound has a peptidase inhibitory action, is useful as an agent for the prophylaxis or treatment of diabetes and the like, and is superior in efficacy, duration of action, specificity, lower toxicity and the like.
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Page/Page column 128-129
(2010/02/11)
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- Preparation and reductive transformations of vinylogous sulfonamides (β-sulfonyl enamines), and application to the synthesis of indolizidines
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Condensation between the methiodide salts of 1-alkylpyrrolidine-2-thiones and ethyl [(4-methylphenyl)sulfonyl]acetate or 1-[(4-methylphenyl)sulfonyl]propan-2-one afforded several 2-{[(4-methylphenyl)sulfonyl]methylene}pyrrolidines in good yield. These β-sulfonyl enamines are sufficiently nucleophilic for cyclisation with internal electrophiles to give sulfone-substituted indolizines, potentially useful scaffolds for alkaloid synthesis. The carbon-carbon double bond in vinylogous sulfonamides was reduced stereoselectively either by catalytic hydrogenation or by treatment with sodium borohydride to yield β-sulfonyl amines. The sulfone group in β-acyl-β-sulfonyl enamines could be removed by hydrogenolysis with sodium amalgam in THF-methanol to give enaminones.
- Michael, Joseph P.,De Koning, Charles R.,Malefetse, Tshepo J.,Yillah, Ibrahim
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p. 3510 - 3517
(2007/10/03)
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- Synthesis of substituted quinolines using the dianion addition of N-Boc-anilines and α-tolylsulfonyl-α,β-unsaturated ketones
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A short and versatile synthesis of substituted quinolines is provided. Alkylation of sodium tolylsulfinate with bromomethyl- or chloromethyl ketones generates β-keto sulfones. Knoevenagel condensation of the β-keto sulfones with an aldehyde provides α-tolylsulfonyl-α,β-unsaturated ketones. Michael addition of the dianion of N-Boc-anilines in the presence of CuCN and LiCl with the unsaturated ketone generates a 1,4-adduct, which after deprotection of the Boc group and thermal elimination of the tolyl sulfone provides the quinoline.
- Swenson, Rolf E.,Sowin, Thomas J.,Zhang, Henry Q.
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p. 9182 - 9185
(2007/10/03)
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- Hypervalent iodine in synthesis. 66. One pot preparation of β-keto sulfones by reaction of ketones, [hydroxy(tosyloxy) iodo] benzene, and sodium sulfinates
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One pot reactions of ketones, [hydroxy(tosyloxy)iodo] benzene and sodium sulfinates lead to the formation of the corresponding β-keto sulfones under mild conditions and in good yield.
- Xie,Chen
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p. 3145 - 3149
(2007/10/03)
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- A facile phase-transfer catalysed synthesis of some β-ketosulphones
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Reaction of phenacyl chloride with sodium benzenesulphinate in refluxing alcohol for 10-12 hr results in the formation of phenylsulphonylacetophenone in about 50% yield. However, use of triethyibenzylammonium chloride as phase- transfer catalyst in acetonitrile medium at room temp. gives the product in over 90% yield in 30 min's, reaction time. Optimum conditions are described for the above reaction by changing the solvent, catalyst, temperature and the type of phase-transfer catalysis itself. Using the optimum conditions, several β-ketosulphones have been synthesised in a facile manner by changing the α-haloketone and sulphinate salts.
- Ramaiah,Dubey,Ramanatham,Grossert,Hooper
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p. 297 - 301
(2007/10/03)
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- Alternative approach to the synthesis of optically active β-keto sulfoxides by furylhydroperoxides enantioselective oxidations
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Enantiomerically enriched β-keto sulfoxides are obtainable by an alternative method to the classical reaction of the enantiomerically pure α- sulfinyl anion with esters or by Anderson's synthesis, through Sharpless modified kinetic resolution of racemic β-keto sulfoxides. High e.e.s are achieved by combining asymmetric oxidation and kinetic resolution using furylhydroperoxides as oxidants.
- Lattanzi, Alessandra,Bonadies, Francesco,Schiavo, Annamaria,Scettri, Arrigo
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p. 2619 - 2625
(2007/10/03)
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- On The Reactions of Benzeneseleninic Anhydride With Monosubstituted Hydrazones. Evidence for Radical Pathways.
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The known oxidation of mono-substituted hydrazones by benzeneseleninic anhydride has been studied using 77Se and 13C NMR spectroscopy.The intermediates in the reaction have been identified.Good evidence that certain steps in these reactions are radical in character has been secured.
- Barton, Derek H. R.,Okano, Takashi,Parekh, Shyamal I.
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p. 1823 - 1836
(2007/10/02)
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- HYDRATION OF 1- AND 3-ARYLSULFONYL-1-PROPYNES AND ARYLSULFONYLALLENES
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The reactions of isomeric 1- and 3-arylsulfonyl-1-propynes and arylsulfonylallenes with primary aromatic amines in organic solvent-water system lead to arylsulfonyl-2-propanones.Unstable addition products (enamines) are formed in the reaction and then undergo hydration and are transformed into the ketones.
- Mikhailova, V. N.,Bulat, A. D.,Yurevich, V. P.,Ezhova, L. A.
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p. 1756 - 1759
(2007/10/02)
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