33963-58-5Relevant academic research and scientific papers
Applicability and mathematical verification of the reactivity-selectivity principle in the oxidation of thioanisoles by oxo(salen)manganese(v) complexes
Chellamani, Arunachalam,Alhaji, Naina Mohammed Ismail,Rajagopal, Seenivasan
, p. 299 - 302 (1997)
The second-order rate constants for the oxidation of various para-substituted thioanisoles with substituted oxo(salen)manganese(v) complexes have been measured spectrophotometrically in acetonitrile at 25°C. Electron-withdrawing substituents in thioanisol
Electron transfer reactions of iron (III) - Polypyridyl complexes with organic sulphides
Balakumar, Subramaniam,Thanasekaran, Pounraj,Rajagopal, Seenivasan,Ramaraj, Ramasamy
, p. 4801 - 4818 (1995)
The redox reactions of FeL33+ (where L = 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridine and 1,10-phenanthroline) with alkyl aryl sulphides in aqueous methanol have been studied by the spectrophotometric technique. The comparison of t
Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
Zhao, Bin,Hammond, Gerald B.,Xu, Bo
supporting information, (2021/09/13)
We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
Electrochemical Scalable Sulfoxidation of Sulfides with Molecular Oxygen and Water
Cheng, Zhen,Gao, Xinglian,Yao, Lingling,Wei, Zhaoxin,Qin, Guohui,Zhang, Yonghong,Wang, Bin,Xia, Yu,Abdukader, Ablimit,Xue, Fei,Jin, Weiwei,Liu, Chenjiang
, p. 3743 - 3747 (2021/07/26)
An efficient and chemoselective synthesis of sulfoxides through the electrooxidation of sulfides has been well developed. This protocol takes advantage of electricity as the terminal oxidant and of molecular oxygen and water as the oxygen atom sources. A variety of structurally diverse sulfoxide compounds are assembled in moderate to excellent yields. The scaled-up reactions at 6–20 mmol show the good practicability and application potential of this methodology. A possible free radical mechanism has been proposed to rationalize the reaction procedure.
Switchable Synthesis of Aryl Sulfones and Sulfoxides through Solvent-Promoted Oxidation of Sulfides with O2/Air
Cheng, Zhen,Sun, Pengchao,Tang, Ailing,Jin, Weiwei,Liu, Chenjiang
supporting information, p. 8925 - 8929 (2019/11/14)
A practical and switchable method for the synthesis of aryl sulfones and sulfoxides via sulfide oxidation was developed. The chemoselectivities of products were simply controlled by reaction temperature using O2/air as the terminal oxidant and oxygen source. The broad substrate scope, easy realization of gram-scale production, and the simplification of a sulfide oxidation system render the strategy attractive and valuable.
Cytochrome P450 CYP199A4 from Rhodopseudomonas palustris Catalyzes Heteroatom Dealkylations, Sulfoxidation, and Amide and Cyclic Hemiacetal Formation
Coleman, Tom,Wong, Siew Hoon,Podgorski, Matthew N.,Bruning, John B.,De Voss, James J.,Bell, Stephen G.
, p. 5915 - 5927 (2018/05/29)
The cytochrome P450 enzymes execute a range of selective oxidative biotransformations across many biological systems. The bacterial enzyme CYP199A4 catalyzes the oxidative demethylation of 4-methoxybenzoic acid. The benzoic acid moiety of the molecule binds in the active site of the enzyme such that the functional group at the para-position is held close to the heme iron. Therefore, CYP199A4 has the potential to catalyze alternative monooxygenase reactions with different para-substituted benzoic acid substrates such as thioethers and alkylamines. The oxidation of 4-methyl- and 4-ethyl-thiobenzoic acids by CYP199A4 resulted in sulfur oxidation. 4-Ethylthiobenzoic acid sulfoxidation and 4-ethylbenzoic acid hydroxylation by CYP199A4 occurred with high enantioselectivity (>74% enantiomeric excess). By way of contrast, CYP199A4 catalyzed exclusive oxidative N-demethylation over N-oxide formation with 4-methyl- and 4-dimethylaminobenzoic acids. Unexpectedly acetamide formation by CYP199A4 competes with dealkylation in the turnover of 4-ethyl- and diethyl-aminobenzoic acids. No oxidative dealkylation was observed with 3,4-ethylenedioxybenzoic with only hydroxylation to form a cyclic hemiacetal being detected. The X-ray crystal structures of four substrate-bound forms of the enzyme were solved and revealed subtle changes in the location of the para substituent which, when combined with the reactivity of the substituents, provided a basis for understanding the changes in selectivity. Furthermore, in the 4-ethylthiobenzoic acid-bound structure, the active site residue Phe298 moves to accommodate the substituent which points away from the heme iron. As such, the CYP199A4 enzyme provides ready access to a combination of structural, binding, and activity data with which to study a variety of reactions which are catalyzed by the P450 superfamily of enzymes.
Selective sulfoxidation with hydrogen peroxide catalysed by a titanium catalyst
Postigo, Lorena,Ventura, Maria,Cuenca, Toms,Jimnez, Gerardo,Royo, Beatriz
, p. 320 - 324 (2015/02/02)
A moisture-tolerant cyclopentadienyl-silsesquioxane titanium complex efficiently catalyses the selective oxidation of various types of sulfides to either sulfoxides (TOFs up to 32 530 h-1) or sulfones with H2O2 (30% in water) under mild conditions.
Electron-deficient heteroarenium salts: An organocatalytic tool for activation of hydrogen peroxide in oxidations
?turala, Ji?í,Bohá?ová, Soňa,Chudoba, Josef,Metelková, Radka,Cibulka, Radek
, p. 2676 - 2699 (2015/03/18)
A series of monosubstituted pyrimidinium and pyrazinium triflates and 3,5-disubstituted pyridinium triflates were prepared and tested as simple catalysts of oxidations with hydrogen peroxide, using sulfoxidation as a model reaction. Their catalytic efficiency strongly depends on the type of substituent and is remarkable for derivatives with an electron-withdrawing group, showing reactivity comparable to that of flavinium salts which are the prominent organocatalysts for oxygenations. Because of their high stability and good accessibility, 4-(trifluoromethyl)pyrimidinium and 3,5-dinitropyridinium triflates are the catalysts of choice and were shown to catalyze oxidation of aliphatic and aromatic sulfides to sulfoxides, giving quantitative conversions, high preparative yields and excellent chemoselectivity. The high efficiency of electron-poor heteroarenium salts is rationalized by their ability to readily form adducts with nucleophiles, as documented by low pKR+ values (pKR+ red > -0.5 V). Hydrogen peroxide adducts formed in situ during catalytic oxidation act as substrate oxidizing agents. The Gibbs free energies of oxygen transfer from these heterocyclic hydroperoxides to thioanisole, obtained by calculations at the B3LYP/6-311++g(d,p) level, showed that they are much stronger oxidizing agents than alkyl hydroperoxides and in some cases are almost comparable to derivatives of flavin hydroperoxide acting as oxidizing agents in monooxygenases.
Kinetics and mechanism of (salen)MnIII catalyzed oxidation of methyl phenyl sulfides with sodium metaperiodate
Chellamani, Arunachalam,Subramanian, Ramasamy
, p. 1584 - 1590 (2014/01/23)
The kinetics of (salen)MnIII complexes-catalyzed oxidation of phenyl methyl sulfides with periodate in 90% acetonitrile-10% water (v/v) mixture at 20 °C has been studied spectrophotometrically. The oxidation follows an overall second order kine
Metal-free highly efficient aerobic oxidation of sulfides to sulfoxides catalyzed by DBDMH/TBN/H2O
Zhang, Hua,Chen, Chunyu,Liu, Renhua
experimental part, p. 811 - 819 (2012/01/17)
A highly efficient metal-free catalytic system, 1,3-dibromo-5,5- dimethylhydantoin (DBDMH)-tert-butylnitrite (TBN)-H2O, has been developed for an environmentally friendly and economical aerobic acid-free oxidation of sulfides. TBN was identifie
