- 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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- Controlled Synthesis of β-Keto Sulfones and Vinyl Sulfones under Electrochemical Oxidation
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Selective sulfonylation and oxosulfonylation of alkenes with sulfinates have been developed via anodic oxidation in an undivided cell. The novel electrosynthetic method provided β-keto sulfones and vinyl sulfones with good to excellent yields in the absence of any transition metal catalyst and oxidants. Mechanism studies show that two different pathways involved in these two transformations.
- Fang, Yang,Xu, Dongping,Yu, Yingliang,Tang, Rumeng,Dai, Shuaishuai,Wang, Zhenghua,Zhang, Wu
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- A glucose oxidase-hemoglobin system for efficient oxysulfonylation of alkenes/alkynes in water
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Background: β-ketosulfones are important bioactive compounds that have been extensively studied in organic chemistry. In this work, a green and efficient process for the synthesis of β-ketosulfones from alkenes (1) or alkynes (3) with sodium benzenesulfinate (2) was developed. Results: Under optimal conditions (alkenes (0.5 mmol) or alkynes (0.5 mmol), sodium benzenesulfinate (0.5 mmol), water (2 mL), hemoproteins (heme concentration: 0.06 mol%), GOX (42 U/ml), room temperature, 2 h), high yields of β-ketosulfones could be obtained when HgbRb (hemoglobin from rabbit blood) and GOX (glucose oxidase from Aspergillus niger) was used as the catalyst. Conclusion: This enzymatic method demonstrates the great potential for the synthesis of β-ketosulfones and extends the application of dual protein systems in organic synthesis.
- Li, Chen,Li, Fengxi,Li, Zhengqiang,Liu, Jiaxu,Su, Jiali,Wang, Chunyu,Wang, Lei,Xu, Yaning,Yu, Yue
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- Oxidative Sulfonylation of Hydrazones Enabled by Synergistic Copper/Silver Catalysis
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A copper/silver-cocatalyzed protocol for oxidative sulfonylation of hydrazones is demonstrated. A wide range of β-ketosulfones and N-acylsulfonamides are directly synthesized in moderate to good yields. Our work provides a viable method for scalable preparation of β-ketosulfone derivatives that have found wide applications in the pharmaceutical industry.
- Xu, Jun,Shen, Chao,Qin, Xian,Wu, Jie,Zhang, Pengfei,Liu, Xiaogang
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p. 3706 - 3720
(2021/02/05)
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- NBS-mediated synthesis of β-keto sulfones from benzyl alcohols and sodium arenesulfinates
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An efficient synthetic route towards the synthesis of β-keto sulfones has been developed from secondary benzyl alcohols using N-bromosuccinimide (NBS). The present protocol utilizes NBS as oxidant as well as brominating agent, readily accessible benzyl alcohols and sodium arenesulfinates as the sulfonylating reagent under mild conditions. The control experiments revealed that the reaction proceeds via oxidation of alcohol to ketone, α-bromination of ketone and nucleophilic substitution by sodium arenesulfinate. Furthermore, the efficiency of the methodology was tested with a gram scale reaction and also shown the synthetic utility.
- Muneeswara, Madithedu,Sundaravelu, Nallappan,Sekar, Govindasamy
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p. 3479 - 3484
(2019/05/21)
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- Method for synthesizing alpha-sulfone ketone compound from alpha, alpha-dibromo ketone by one-pot process
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The invention discloses a method for synthesizing a high-added-value alpha-sulfone ketone compound from an alpha, alpha-dibromo ketone compound by a one-pot process. The method has the advantages thatan alpha-sulfone ketone derivative is synthesized from alpha, alpha-dibromo ketone, which is simple and easy to obtain, by the one-pot process without separation of an alpha-bromo ketone intermediate, so that a separation process for an intermediate product is omitted, the steps are reduced, and requirements for environment protection are met; the steps of the method are simple and easy to operate, no transition metal reagents are required, and economical sulfonate with less pollution is directly used as a promoter and a sulfonating agent for reducing debromination of the alpha, alpha-dibromoketone, so that the cost is reduced, and economic benefits of reactions are increased; a system for preparing the alpha-sulfone ketone derivative by the one-pot process is developed to provide a novel synthesis method for preparation of the alpha-sulfone ketone compound, and the method has good industrialization prospect and potential application value.
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Page/Page column 17
(2019/10/17)
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- Highly enantioselective transfer hydrogenation of racemic α-substituted β-keto sulfonamides: Via dynamic kinetic resolution
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Highly enantioselective transfer hydrogenation of β-keto sulfonamides was developed via dynamic kinetic resolution using a chiral Ru(ii) catalyst with an azeotropic solution of HCO2H/Et3N as a hydrogen donor, affording α-substituted β-hydroxyl sulfonamides in good yields with excellent diastereo- and enantioselectivities. This method is featured with mild conditions, easy operation, and a broad substrate scope, which make it possible to find wide applications in the synthesis of natural products and biologically active compounds containing the α-substituted β-hydroxyl sulfonamide core.
- Xiong, Zhichao,Pei, Chengfeng,Xue, Peng,Lv, Hui,Zhang, Xumu
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supporting information
p. 3883 - 3886
(2018/04/20)
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- MANUFACTURING METHOD OF COMPOUND HAVING SULFONYL GROUP
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The present invention relates to a method for manufacturing a compound having a sulfonyl group, which includes a step for reacting thiosulfonates in a solvent comprising nucleophilic bases with an electrophilic agent. Accordingly, the present invention can manufacture the compound having the sulfonyl group with a variety of structures with high efficiency and high yield through more simplified processes than conventional methods.COPYRIGHT KIPO 2018
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Paragraph 0108; 0109; 0121-0124
(2018/10/03)
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- Synthesis of Sulfones and Sulfonamides via Sulfinate Anions: Revisiting the Utility of Thiosulfonates
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Simple and high-yielding strategies for the production of a variety of sulfones and sulfonamides, using thiosulfonates synthesized by copper-catalyzed aerobic dimerization, are reported. Although thiosulfonates are an old class of compound, practical methods for their synthesis and utilization have not been rigorously developed. In this study, we revisit the reactions of easily accessible thiosulfonates to form sulfinate anions. Because of the similar reactivity of thiosulfonates and metal sulfinates derived from toxic SO2, thiosulfinates are proposed to be stable, nontoxic alternatives to metal sulfinate salts.
- Shyam, Pranab K.,Jang, Hye-Young
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p. 1761 - 1767
(2017/02/10)
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- Operando X-ray absorption and EPR evidence for a single electron redox process in copper catalysis
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An unprecedented single electron redox process in copper catalysis is confirmed using operando X-ray absorption and EPR spectroscopies. The oxidation state of the copper species in the interaction between Cu(ii) and a sulfinic acid at room temperature, and the accurate characterization of the formed Cu(i) are clearly shown using operando X-ray absorption and EPR evidence. Further investigation of anion effects on Cu(ii) discloses that bromine ions can dramatically increase the rate of the redox process. Moreover, it is proven that the sulfinic acids are converted into sulfonyl radicals, which can be trapped by 2-arylacrylic acids and various valuable β-keto sulfones are synthesized with good to excellent yields under mild conditions.
- Lu, Qingquan,Zhang, Jian,Peng, Pan,Zhang, Guanghui,Huang, Zhiliang,Yi, Hong,Miller, Jeffrey T.,Lei, Aiwen
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p. 4851 - 4854
(2015/07/27)
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- Aerobic oxysulfonylation of alkenes using thiophenols: An efficient one-pot route to β-ketosulfones
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We have developed a highly efficient synthetic route to β-ketosulfones via AgNO3 catalyzed oxysulfonylation of alkenes using thiophenols in the presence of air (O2) and K2S2O8 as eco-friendly oxidants. Thiophenols have been used as sulfonylation precursors for the first time in a dioxygen activation based radical process. Moreover, the protocol also offers a new and convenient method for the synthesis of β-hydroxysulfides at room temperature without the use of any initiator. This journal is
- Singh, Atul K.,Chawla, Ruchi,Keshari, Twinkle,Yadav, Vinod K.,Yadav, Lal Dhar S.
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supporting information
p. 8550 - 8554
(2014/12/10)
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- Iron-catalyzed direct difunctionalization of alkenes with dioxygen and sulfinic acids: A highly efficient and green approach to β-ketosulfones
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A novel iron-catalyzed direct difunctionalization of alkenes with sulfinic acids and dioxygen for the synthesis of β-ketosulfones has been developed under mild conditions. The present protocol, which utilizes an inexpensive iron salt as the catalyst, readily available benzenesulfinic acids as the sulfonylating reagents, and dioxygen as the oxidant and oxygen source, provides a cost-effective and environmentally benign approach to access various β-ketosulfones.
- Wei, Wei,Wen, Jiangwei,Yang, Daoshan,Wu, Min,You, Jinmao,Wang, Hua
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supporting information
p. 7678 - 7681
(2014/12/10)
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- Aerobic oxidation in nanomicelles of aryl alkynes, in water at room temperature
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On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes to β-ketosulfones has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors. It's all happenin' in the micelle! The highly preferential dissolution of oxygen gas within the lipophilic cores inside nanomicelles leads to efficient trapping of in situ generated vinyl radicals. These intermediate radicals, derived from arylalkynes and sulfinic acids, lead to β-ketosulfone products, formed under especially mild and green conditions: no metals, no heating or cooling, recyclable aqueous media, and low E Factors.
- Handa, Sachin,Fennewald, James C.,Lipshutz, Bruce H.
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supporting information
p. 3432 - 3435
(2014/04/03)
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- Aerobic oxysulfonylation of alkynes in aqueous media: Highly selective access to β-keto sulfones
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The first application of inexpensive commercially available sulfinate salts to produce β-keto sulfones directly from alkynes via aerobic oxysulfonylation has been developed. It is a highly selective (undesired Glaser-Hay homo-coupling and ATRA process totally suppressed) general method of functionalization of alkynes on water at room temperature involving FeCl 3/K2S2O8 catalyzed formation of sulfonyl radicals from sulfinate salts.
- Singh, Atul K.,Chawla, Ruchi,Yadav, Lal Dhar S.
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p. 2845 - 2848
(2014/05/06)
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- K2S2O8-mediated aerobic oxysulfonylation of olefins into β-Keto sulfones in aqueous media
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β-Keto sulfones were obtained in good to excellent yields (73-94%) directly from unactivated olefins by employing inexpensive sodium arenesulfinate salts as sulfonylating agents and K2S2O8 as a radical initiator in open flasks and aqueous media at room temperature under transition-metal-free conditions. The reported oxidative sulfonylation protocol is highly practical and environmentally benign, as self-manifested by the extremely mild reaction conditions. Copyright
- Chawla, Ruchi,Singh, Atul K.,Yadav, Lal Dhar S.
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supporting information
p. 2032 - 2036
(2014/04/17)
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- Copper-catalyzed direct oxysulfonylation of alkenes with dioxygen and sulfonylhydrazides leading to β-ketosulfones
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The first copper-catalyzed oxysulfonylation reaction of alkenes with dioxygen and sulfonylhydrazides for the construction of β-ketosulfones has been developed under mild conditions without any ligand or additive.
- Wei, Wei,Liu, Chunli,Yang, Daoshan,Wen, Jiangwei,You, Jinmao,Suo, Yourui,Wang, Hua
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supporting information
p. 10239 - 10241
(2013/10/22)
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- Dioxygen-triggered oxidative radical reaction: Direct aerobic difunctionalization of terminal alkynes toward β-keto sulfones
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An unprecedented dioxygen-triggered oxidative radical process was explored using dioxygen as the solely terminal oxidant, realizing aerobic oxidaitve difunctionalization of terminal alkynes toward β-keto sulfones with high selectivity. Operando IR experiments revealed that pyridine not only acts as a base to successfully surpress ATRA (atom transfer radical addition) process, but also plays a vital role in reducing the activity of sulfinic acids.
- Lu, Qingquan,Zhang, Jian,Zhao, Ganglu,Qi, Yue,Wang, Huamin,Lei, Aiwen
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supporting information
p. 11481 - 11484
(2013/09/02)
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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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- 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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- Stereochemical studies on the formation of α,β-epoxysulfones using α-chloro-β-hydroxysulfones of known configuration
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Substitution reactions adjacent to sulfonyl groups are known to proceed with difficulty, and there is evidence to suggest that these may not necessarily proceed by an SN2 pathway.The mechanism of these reactions could be studied in principle by using the conversion of α-chloro-β-hydroxysulfones of known configuration into α,β-epoxysulfones of known configuration.This paper describes results in which this has been attempted.However, the stereochemical aspects of the epoxide formation could not be assigned unequivocally because of the intervention of a very facile "retro-aldol" process when the chlorohydrins are subjected to treatment with bases, although the experimental results do suggest that the reaction does proceed in a regular SN2-like manner, with inversion at carbon.The X-ray crystal structures of two highly substituted α,β-epoxysulfones are presented, thus putting the structures, including stereochemistry, of a range of these compounds of firm ground.
- Grossert, J. Stuart,Sotheeswaran, Subramanian,Dharmarante, H. Ranjith W.,Cameron, T. Stanley
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p. 2870 - 2879
(2007/10/02)
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- Vinyl Sulfone Bicycloannulation of Cyclohexenones: One-Step Synthesis of Tricyclo2,7>octan-6-ones
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Vinyl sulfones bicycloannulate the α'-enolates of α-cyclohexenones in the presence of hexamethylphosphoramide in refluxing tetrahydrofuran to give tricyclo2,7>octan-6-ones in a single synthetic step.In the case of β-methylcyclohexenones this method gives higher yields than vinylphosphonium bicycloannulation, but with α-methylcyclohexenones theopposite is true.The reaction is successful with both aryl vinyl sulfones and aryl isopropenyl sulfones, but the presence of electron-withdrawing para substituents on the aromatic ring was found to be disadvantageous.Based on the isolation of intermediates and side products, the mechanism of the bicycloannulation is believed to proceed via sequential conjugate addition of the enolate to the vinyl sulfone, intramolecular Michael addition, and expulsion of arene sulfinate anion with formation of the cyclopropane ring.
- Cory, Robert M.,Renneboog, Richard M.
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p. 3898 - 3904
(2007/10/02)
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