Vinyl sulfones in solid-phase synthesis: preparation of 4,5,6,7-tetrahydroisoindole derivatives

The preparation of functionalized 4,5,6,7-tetrahydroisoindole via a traceless solid-phase sulfone linker strategy is described. Thermolytic extrusion of SO(2) from polymer-bound 3-(phenylsulfonyl)-3-sulfolene (7) generated polymer-bound 2-(phenylsulfonyl)-1,3-butadiene (9) in situ which underwent Diels--Alder cycloaddition with various dienophiles to furnish vinyl sulfone resins 10-14. To complete a traceless linker cleavage strategy, (p-tolysulfonyl)methyl isocyanide or ethyl isocyanoacetate was employed to react with the vinyl sulfone moiety to liberate functionalized 4,5,6,7-tetrahydroisoindole products from the resin. Using this chemistry, nine tetrahydroisoindole derivatives (6, 15-22) were prepared in 32-41% overall yields from polystyrene/divinylbenzene sulfinate 1.     

Vinyl sulfones as SEI-forming additives in propylene carbonate based electrolytes for lithium-ion batteries

The electrochemical performance of propylene carbonate (PC) based electrolytes with methyl vinyl sulfone (MVS) and ethyl vinyl sulfone (EVS) as film-forming additives on graphite electrode was studied. The results indicate that already small amount of these additives is able to form a stable SEI and thus successfully prevent exfoliation of the graphite. Moreover, the tested additives showed slight impact on the cathode performance as well as on the safety characteristics.     

Vinyl bis-sulfone methodology in thiosugars: selective access to chiral thiovinyl sulfones and PSE oxathianes

Based on the vinyl bis-sulfone methodology previously developed to synthesize PSE acetals, an original approach to homochiral carbohydrate-derived PSE 1,3-oxathianes is described. The ready formation of intermediate phenylsulfonylvinyl sulfides, which have a synthetic potential of their own, emphasizes the versatility of the method.     

Efficient conversion of sulfones into beta-keto sulfones by N-acylbenzotriazoles

Acyclic sulfones 4a-f and alicyclic sulfone 7 react with readily available N-acylbenzotriazoles 3a-g (derived from aliphatic, aromatic, and heteroaromatic carboxylic acids) to provide the corresponding beta-keto sulfones 5a-n and 8a-c, respectively, in good to excellent yields.     

Vinyl sulfones: inhibitors of SrtA, a transpeptidase required for cell wall protein anchoring and virulence in Staphylococcus aureus

Several small molecule vinyl sulfones were found to exhibit irreversible time-dependent inhibition of the Staphylococcus aureus sortase SrtA in vitro. A representative of these compounds was shown to impair the ability of S. aureus bacteria to bind fibronectin-coated surfaces through in vivo inhibition of SrtA-mediated linkage of fibronectin to the cell surface. These data highlight the potential use of small molecule vinyl sulfones as chemotherapeutics to prevent adhesion to and colonization of host tissues during S. aureus infection.     

Aryl aminoalkyl sulfones

Two methods are proposed for the preparation of aryl aminoalkyl sulfones substituted in the aromatic ring: a method based on the oxidation of aryl aminoalkyl sulfides by hydrogen peroxide or of their bases in the presence of HClO₄ and a method based on the oxidation of aryl -chloroalkyl sulfides to chlorosulfones by hydrogen peroxide followed by their condensation with amines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2580–2585, November, 1989.     

Organic synthesis with sulfones XXXII. A convenient route to α,β -unsaturated sulfones from saturated sulfones.

α-sulfonyl litiated anions are oxidized by cupric carboxylates into β, β-unsaturated sulfones. Primary sulfones lead to pure trans-vinylic sulfones.     

Electrochemical fluorination of sulfones

Conclusions Perflurodiethylsulfone and perfluoroethanesulfonyl fluoride are obtained during electrochemical fluorination of diethylsulfone. In the case of tetramethylenesulfone one C — S bond is broken and perfluorobutanesulfonyl fluoride is formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 945–947, April, 1969.     

Acetylenic sulfones and sulfoxides

Russian Chemical Bulletin -     

Cyclopropanation of Vinyl Sulfides and Vinyl Sulfones

Cyclopropanation of vinyl sulfones and vinyl sulfides can be achieved by phase transfer catalysis where other cyclopropanation methods have failed.     

Tautomerism in some quinaldyl sulfones

A series of quinaldyl sulfones was synthesized and their tautomeric composition was determined by ¹H nmr.     

Syntheses of Vinyl Sulfoxide/Vinyl Acetate-Type Copolymers

The homopolymerization of a series of alkyl vinyl sulfoxides (CH₂[dbnd]CHSOR; R = CH₃ (MVSO), C₂H₅ (EVSO), t-C₄H₉ (BVSO)) and their copolymerization with vinyl acetate (VAc) with 2,2′-azobisisobutyronitrile (AIBN) as initiator at 60°C was attempted. MVSO was found to homopolymerize radically, but EVSO and BVSO were not. Poly-MVSO is soluble in chloroform, methanol, DMSO, and water, but insoluble in acetone and benzene. MVSO and EVSO were found to copolymerize with VAc, but BVSO was not. The copolymerization parameters obtained for both systems were as follows; r₁(MVSO) = 2.23, r₂ (VAc) = 0.09, and r₁(EVSO) = 3.40, r₂ (VAc) = 0.11, respectively. MVSO/vinyl alcohol (VA) copolymers were obtained through the saponification of MVSO/VAc copolymers by sodium hydroxide in methanol. The solubility of MVSO/VAc and of MVSO/VA copolymers toward various solvents was examined, and it was observed that the sulfoxide comonomer has a tendency to give amphiphilicit to poly(vinyl acetate) and poly(vinyl alcohol). The 24 mol% MVSO containing VAc copolymer is soluble in both benzene and water.     

Pendant functional group copolyether sulfones: III. Modified copolyether sulfones with bisphenolic copper chelate

New copolyether sulfones having copper(II) chelate units as pendant groups were synthesized by a chemical modification reaction of chloromethylated polysulfones with the sodium salt of copper(II) bis(2,4‐dihydroxybenzaldehyde) in dichloromethane/dimethyl sulfoxide as solvent system, at room temperature. The resulting copolymers were confirmed by IR absorption spectra and characterized by softening points, solubilities, differential scanning calorimetry and thermogravimetric analysis measurements. A slow increase of glass transition temperature values was observed in comparison with the starting chloromethylated polysulfones, and the thermal stability in air showed a slow, but insignificant, decrease. A significant increase in solvent resistance was observed. The glass transition temperature values, which do not exceed 200 °C, provide processing possibilities. Copyright © 2003 John Wiley & Sons, Ltd.     

Cyclodimerizations and Copolymerizations of Vinyl Ketones with Vinyl Monomers

Stable high-molecular-weight polyacetals can be prepared from formaldehyde or from its trimer trioxane.