5366-49-4Relevant articles and documents
Facile One-Pot Access to α-Diazo-β-ketosulfones from Sulfonyl Chlorides and α-Haloketones
Dar'In, Dmitry,Kantin, Grigory,Bakulina, Olga,Krasavin, Mikhail
, p. 2259 - 2266 (2020/08/26)
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.
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
Lozovskiy, Stanislav V.,Ivanov, Alexander Yu.,Khoroshilova, Olesya V.,Vasilyev, Aleksander V.
, p. 2897 - 2906 (2018/12/13)
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.
Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C?S Bond Cleavage: Reaction Development and Mechanism Study
Du, Bingnan,Wang, Wenmin,Wang, Yang,Qi, Zhenghang,Tian, Jiaqi,Zhou, Jie,Wang, Xiaochen,Han, Jianlin,Ma, Jing,Pan, Yi
supporting information, p. 404 - 408 (2018/02/21)
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.
