3112-85-4Relevant articles and documents
1,1′-Binaphthyl-2-methylpyridinium-based peroxophosphotungstate salts: Synthesis, characterization and their use as oxidation catalysts
Jahier, Claire,Felpin, Francois-Xavier,Meliet, Catherine,Agbossou-Niedercorn, Francine,Hierso, Jean-Cyrille,Nlate, Sylvain
, p. 5148 - 5155 (2009)
A series of 1,1'-binaphthyl-2-methylammonium and pyridinium salts 6, 7, and 8 was synthesized through the coupling reaction of 2-(bromomethyl)-1,1'- binaphthalene (5) with the dendritic tetraallyl pyridinedicarbinol dendron 2 as well as triethylamine and 4-tert-butylpyridine. Tetraallyl pyridinedicarbinol dendron 2 was prepared by allylation of commercially available diethyl pyridine-3,5-dicarboxylate (1). The allylation of 2 with, allyltrimethylsilane in the presence of boron trifluoride was unsuccessful, as tetraallyl pyridinedicarbinol trifluoroboron adduct 3 was obtained instead of expected hexaallylpyridine compound 4. The catalytic hydrogenation of allyl groups of the ammonium salt of 2, namely, tetraallyl 1,1'-binaphthyl-2-methylpyridinium salt 6, successfully led to the corresponding tetra-n-propyl 1,1'-binaphthyl-2- methylpyridinium salt 9. The reaction between salts 7, 8, and 9 and the heteropolyacid H3PW12O40 in the presence of a large excess of hydrogen peroxide afforded the corresponding 1,1'-binaphthyl-2-methylammonium-based polyoxometalate salts 10, 11, and 12, which, contain a catalytically active trianionic [H3PW 12O4O]3- in the core. These binaphthyl-POM salts are soluble in commonly used organic solvents, and their IR and 31P NMR spectroscopic and elemental analysis data indicate the presence of the POM unit in the frameworks. These POM hybrids are efficient, recoverable, and reusable catalysts in the oxidation of thioanisole, cyclooctene, and cyclohexanol, with H2O2 as the oxidant. A study of the countercation effects indicated that the reaction kinetics and the selectivity are sensitive to the structure of the cation. Two cycles of catalytic reactions were performed without a discernible loss in activity. Wiley-VCH Verlag GmbH & Co. KGaA.
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Field,Clark
, p. 1129 (1957)
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ONE ELECTRON TRANSFER MECHANISM IN THE ENZYMATIC OXYGENATION OF SULFOXIDE TO SULFONE PROMOTED BY A RECONSTITUTED SYSTEM WITH PURIFIED CYTOCHROME P-450
Watanabe, Yoshihito,Iyanagi, Takashi,Qae, Shigeru
, p. 533 - 536 (1982)
A kinetic study on enzymatic S-oxygenation of sulfoxides to sulfones was carried out by a reconstituted system with purified cytochrome P-450.A linear correlation observed between log(Vmax)'s and the one-electron oxidation potentials of sulfoxides suggests that the oxygenation of sulfoxides proceeds via one electron transfer process to the active "oxenoid" intermediate of the enzyme.
Kinetics and mechanism of oxidation of aryl methyl sulfoxides with (salen)MnIII/H2O2 catalytic system
Chellamani, Arunachalam,Sengu, Paramasivan,Alhaji, Naina Mohamed Ismail
, p. 104 - 110 (2010)
The kinetics of (salen)MnIII complexes-catalysed oxidation of aryl methyl sulfoxides with hydrogen peroxide in 80% acetonitrile-20% water solvent mixture at 25 °C has been followed spectrophotometrically. The reaction is first-order in (salen)MnIII, zero-order in hydrogen peroxide and fractional-order in sulfoxide. Also, it has been found that nitrogenous bases affect the oxidation, while free-radical inhibitor does not. However, an increase in the water content of the solvent mixture causes an increase in the rate of reaction. Stoichiometry between H2O2 and sulfoxide has been found to be 1:1 and the product analysis confirms the formation of sulfone and the regeneration of (salen)MnIII complex. These observations have been well analyzed in favor of a Michaelis-Menten type mechanism, involving a manganese(III)-hydroperoxide complex as the reactive species. Using the derived rate law, the oxidant-substrate complex formation constant, K and the oxidant-substrate complex decomposition rate constant, k2 have been evaluated. The proposed mechanism has been well supported by electronic-oxidant and electronic-substrate effect studies.
Trifluoromethyl substituted N-phosphinoyloxaziridines: Organic oxidants with enhanced reactivity
Jennings, W.Brian,O'Shea, John H.,Schweppe, Adrian
, p. 101 - 103 (2001)
New N-phosphinoyloxaziridines containing a trifluoromethyl group at the 3-position are reported. Comparative studies of the rate of oxidation of methyl phenyl sulphoxide to methyl phenyl sulphone indicate that the presence of the CF3 group greatly enhances the oxidising power of N-phosphinoyl (and N-sulphonyl) oxaziridines.
Microwave-assisted Cu-catalyzed protodecarboxylation of aromatic carboxylic acids
Goossen, Lukas J.,Manjolinho, Filipe,Khan, Bilal A.,Rodriguez, Nuria
, p. 2620 - 2623 (2009)
An effective protocol has been developed that allows the smooth protodecarboxylation of diversely functionalized aromatic carboxylic acids within 5-15 min. In the presence of at most 5 mol % of an inexpensive catalyst generated in situ from copper(I) oxide and 1,10-phenanthroline, even nonactivated benzoates were converted in high yields and with great preparative ease.
ON PHENYLSULFINYL CARBENIUM ION
Venier, Clifford G.,Wing, Feagin A. Jr.,Barager, Howard J.
, p. 3159 - 3162 (1980)
Phenylsulfinyl carbenium ion, generated by the acid-catalyzed decomposition of phenyl diazomethyl sulfoxide or the silver-assisted solvolysis of phenyl iodomethyl sulfoxide, is trapped by hydroxylic solvents to yield phenyl methyl sulfone.The possibility of the intermediacy of either phenylsulfinyl carbene or phenylsulfinylmethyl acetate has been ruled out.
High Chemoselectivity in the Construction of Aryl Methyl Sulfones via an Unexpected C-S Bond Formation between Sulfonylhydrazides and Dimethyl Phosphite
Liu, Teng,Yu, Shiwen,Shen, Xiang,Li, Yixian,Liu, Jianjun,Huang, Chao,Cheng, Feixiang
, p. 153 - 160 (2021/10/04)
A highly chemoselective route to aryl methyl sulfones via an unexpected C S bond formation between sulfonylhydrazides and dimethyl phosphite catalyzed by NaI under mild conditions has been established. This transformation provides an alternative and metal-free pathway to acquire various aryl methyl sulfones in good to excellent yields. Notably, dimethyl phosphite was employed as a stable and readily available alkyl source.
A mild and chemoselective CALB biocatalysed synthesis of sulfoxides exploiting the dual role of AcOEt as solvent and reagent
Anselmi, Silvia,Liu, Siyu,Kim, Seong-Heun,Barry, Sarah M.,Moody, Thomas S.,Castagnolo, Daniele
supporting information, p. 156 - 161 (2021/01/14)
A mild, chemoselective and sustainable biocatalysed synthesis of sulfoxides has been developed exploiting CALB and using AcOEt with a dual role of more environmentally friendly reaction solvent and enzyme substrate. A series of sulfoxides, including the drug omeprazole, have been synthesised in high yields and with excellent E-factors.
