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Relevant academic research and scientific papers

Intermolecular Stereoselective Pummerer Reactions of 4-(p-Chlorophenyl)thiane 1-Oxides and trans-1-Thiadecalin 1-Oxides and 2-Thiadecalin 2-Oxides with Acetic Anhydride

The Pummerer reactions of cnformationally fixed 4-(p-chlorophenyl)thiane 1-oxides and trans-1-thiadecalin 1-oxides and trans-2-thiadecalin 2-oxides with acetic anhydride are either stereoselective or stereospecific, both in the absence and in the presence of a scavenger of acetic acid formed, such as dicyclohexylcarbodiimide (DCC) or 2,6-lutidine.However, the 18O-tracer experiments with the 18O-labeled sulfoxide revealed the reaction to be an intermolecular rearrangement, while the kinetic experiment with α-deuterated 4-(p-chlorophenyl)thiane 1-oxides gave sizable values of kinetic isotope effect, i.e., 2.8 for the cis isomer and 3.4 for the trans isomer.In the reaction of 4-arylthiane 1-oxides with acetic anhydride, the thermodynamically controlled product is axial 2-acetoxy-4-(p-chlorophenyl)thiane while the kinetically controlled product is the equatorial isomer which is formed in the presence of the acid scavenger, DCC.In the Pummerer reaction of the thiadecalins S-oxides the equatorial α-acetoxy sulfides are the preferential products, however, the isomer preference is more pronounced in the reaction with DCC.These observations, along with other pertinent data seem to suggest that the rate-determining step in the Pummerer reaction of these simple heterocyclic sulfoxides is E2 elimination of acetic acid from the acetoxysulfonium intermediates.

Stereochemistry of Oxygenation of Organic Sulphides with Pig Liver Microsomal FAD-containing Mono-oxygenase: Comparison with Cytochrome P-450PB Oxidations

The enantiotopic differentiating ability of pig liver microsomal FAD-containing mono-oxygenase (EC 1.14.13.8) in the oxygenation of nine unsymmetrical sulphides has been investigated.By this enzymatic oxygenation, the sulphides are converted into the corr

STEREOSELECTIVE ELECTROOXIDATION OF A THIANE TO THE CORRESPONDING THIANE OXIDE

Electrochemical oxidation of 4-(p-chlorophenyl)thiane in aqueous organic solvents gave selectively the trans-sulfoxyde by bromium ion mediation.A preferential formation of the cis-sulfoxyde was attained under acidic electrolyses.

THE MECHANISTIC MODE OF OXIDATION OF SUBSTITUTED N,N-DIMETHYLANILINES, THIOANISOLES, AND METHYL PHENYL SULFOXIDES BY 5-ETHYL-4a-HYDROPEROXY-3-METHYL-LUMIFLAVIN (4a-FlEt-OOH)

In the oxidation of the title compounds, 5-ethyl-4a-hydroperoxy-3-methyl-lumiflavin (4a-FlEt-OOH), was found to be an electrophilic oxidant similar to m-chloroperoxybenzoic acid.However, the stereoselectivity of the oxidation of cyclic sulfides to the corresponding sulfoxides by 4a-FlEt-OOH was less pronounced than that of the oxygenation with flavin-containing monooxygenase.

SELECTIVE OXIDATION OF SULFIDE BY ArIO-METALLOPORPHYRIN SYSTEM - AN ENZYME MODEL S-OXIDATION

Various sulfides are easily oxidized selectively to the corresponding sulfoxides in quantitative yields by iodosylarene (ArIO) catalyzed by metalloporphyrin (TPPM(III)Cl (M= Fe, Mn)).The oxidation system is demonstrated to be a possible model for monooxygenase in the study of the stereochemistry of these sulfoxides.Metalloporphyrin-iodosylarene can initially equilibrate with the oxometalloporphyrin (TPPM(V)=O*Cl) formed in situ.The initial process may involve one-electron transfer from the sulfide to the intermediate oxometalloporphyrin followed by coupling of two resulting charged products, and/or nucleophilic attack of sulfide on oxometalloporphyrin oxygen.The overall reactions are depicted by paths with different electron demands from the results of Hammett plots.