3708-04-1Relevant articles and documents
PREFERRED CONFORMATIONS OF METHYLTHIO-ACETONE AND -ACETOPHENONE, METHYLSULPHONYL-ACETONE AND -ACETOPHENONE, FROM MOLECULAR-MECHANICS AND DIPOLE-MOMENT TECHNIQUES
Lumbroso, H.,Bertin, D. M.,Olivato, P. R.,Bonfada, E.,Mondino, M. G.,Hase, Y.
, p. 113 - 122 (1989)
Preferred conformations for the title compounds are determined from calculated molecular-mechanics energies in the gaseous phase and analysis of the dipole moments measured in solvents of low dielectric permittivity.In all cases, the gauche conformer having the Me-S bond situated far away from the Me(-C) (or Ph(-C)) group, and nearly bisecting one of the C(=O)-C-H valleys, is predominant.
Oxidant-free C-H sulfonylation of enamides: Electrochemical synthesis of β-amidovinyl and carbonyl sulfones from sulfonyl hydrazide and enamides
Qi, Liang,Xiao, Linxia,Chen, Xi,Zhang, Ziyi,Shi, Qin,Chen, Jinkang
supporting information, (2021/12/17)
A mild, practical, eco-friendly and environmentally friendly electrochemical synthesis method of β-aminovinyl sulfone and carbonyl sulfones from sulfonyl hydrazide and enamides has been developed. This transformation only requires electrolytes and solvent, thus avoids transition metal catalysts, stoichiometric oxidant and base. Two different types of sulfone derivatives can be obtained only by changing the reaction solvent. This transformation also features mild conditions (room temperature, air), broad substrate scopes, and excellent stereoselectivities in mild to good yield.
Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
Das, Sanju,Mandal, Tanumoy,De Sarkar, Suman
supporting information, p. 755 - 765 (2021/12/10)
A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.
Cu(OTf)2-Catalyzed efficient sulfonylation of vinyl azides with sodium sulfinates
Ning, Zhitao,Xu, Zheng,Liu, Ruikai,Du, Zhengyin
supporting information, p. 3492 - 3500 (2021/10/14)
A simple oxidative cross-coupling reaction between vinyl azides and sodium sulfinates was developed. This reaction uses commercial arylsulfinates that are more efficient, cheaper, and more stable as sulfonylation reagents, for efficiently, cheaply, and environmentally friendly synthesis of β-keto sulfones. And the reaction has the advantages of simple operation, high efficiency, good yield, and also has a wide range of functional group tolerance.
Photosensitizer-free synthesis of β-keto sulfones: Via visible-light-induced oxysulfonylation of alkenes with sulfonic acids
Hong, Yun-Yun,Peng, Sha,Peng, Zhen,Tang, Shan-Shan,Xie, Long-Yong,Xu, Xiang-Qun,Yang, Li-Hua
supporting information, p. 4537 - 4541 (2021/05/31)
A practical and environment-friendly methodology for the construction of β-keto sulfones through visible-light induced direct oxysulfonylation of alkenes with sulfonic acids at ambient temperature under open-air conditions was developed. Most importantly, the reaction proceeded smoothly without the addition of any photocatalyst or strong oxidant, ultimately minimizing the production of chemical waste.
A glucose oxidase-hemoglobin system for efficient oxysulfonylation of alkenes/alkynes in water
Li, Chen,Li, Fengxi,Li, Zhengqiang,Liu, Jiaxu,Su, Jiali,Wang, Chunyu,Wang, Lei,Xu, Yaning,Yu, Yue
, (2020/12/29)
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.
Chemoenzymatic Oxosulfonylation-Bioreduction Sequence for the Stereoselective Synthesis of β-Hydroxy Sulfones
González-Sabín, Javier,Gotor-Fernández, Vicente,López-Agudo, Marina,Lavandera, Iván,Ríos-Lombardía, Nicolás
, (2021/08/23)
A series of optically active β-hydroxy sulfones has been obtained through an oxosulfonylation-stereoselective reduction sequence in aqueous medium. Firstly, β-keto sulfones were synthesized from arylacetylenes and sodium sulfinates to subsequently develop the carbonyl reduction in a highly selective fashion using alcohol dehydrogenases as biocatalysts. Optimization of the chemical oxosulfonylation reaction was investigated, finding inexpensive iron(III) chloride hexahydrate (FeCl3 ? 6H2O) as the catalyst of choice. The selection of isopropanol in the alcohol-water media resulted in high compatibility with the enzymatic process for enzyme cofactor recycling purposes, providing a straightforward access to both (R)- and (S)-β-hydroxy sulfones. The practical usefulness of this transformation was illustrated by describing the synthesis of a chiral intermediate of Apremilast. Interestingly, the development of a chemoenzymatic cascade approach avoided the isolation of β-keto sulfone intermediates, which allowed the preparation of chiral β-hydroxy sulfones in high conversion values (83–94 %) and excellent optical purities (94 to >99 % ee).
Copper-catalyzed aerobic oxidative cross-coupling reactions of vinylarenes with sulfinate salts: A direct approach to β-ketosulfones
Chen, Yu,Xu, Lei,Wang, Biyu,Jiang, Jingjing,Sun, Yixiang,Li, Longchun
, (2021/01/25)
A copper-catalyzed aerobic oxidative cross-coupling reactions for the synthesis of β-ketosulfones via formation of a C[sbnd]S bond has been demonstrated. Promoted by the crucial copper catalyst, perfect selectivity and good to excellent yields could be achieved. This method, including inexpensive copper catalyst, wide functional group tolerance, and open air conditions, make it very attractive and practical. More importantly, it also provides a versatile tool for the construction of β-ketosulfones from basic starting materials under mild conditions.
Method for synthesizing beta-ketosulfone derivative under mild condition and obtained beta-ketosulfone derivative
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Paragraph 0083; 0084, (2021/08/28)
The invention discloses a method for synthesizing a beta-ketosulfone derivative under a mild condition, which comprises the following steps: dissolving aryl olefin and sodium sulfinate in a solvent in a reaction container, adding an acidic additive, sealing the reaction container under the conditions that air exists in the reaction container and no transition metal exists, and purifying after reaction to obtain the beta-ketosulfone derivative. The free radical addition oxidation reaction of olefin and sulfinic acid can be realized under the mild condition without transition metal, the reaction raw materials are cheap and easy to obtain, no organic metal reagent or transition metal is needed, air is used as an oxidizing agent, no dangerous peroxide or persulfide is needed, and the method is compatible with air. The method has the advantages of simple operation and the like, and overcomes the defects of transition metal participation, large catalyst consumption, expensive reagents, high method cost, more reaction steps, more by-products and the like in the prior art.
Dioxygen-Triggered Oxosulfonylation/Sulfonylation of Terminal Olefins toward β-Keto Sulfones/Sulfones
Wang, Yanjie,Zhao, Yuhan,Cai, Changqun,Wang, Lingyun,Gong, Hang
supporting information, p. 8296 - 8301 (2021/11/13)
A dioxygen-triggered oxosulfonylation/sulfonylation of unactivated olefins to achieve β-keto sulfones/sulfones has been developed. Interestingly, pluralistic mechanisms were found when different types of compounds were applied as substrates, and different products were achieved. The reaction is carried out with a high atomic efficiency in the absence of a metal and a catalyst at room temperature under an air atmosphere. Importantly, as a proof-of-concept, a bioactive molecule was synthesized on a gram-scale level using this method.
