119577-18-3Relevant academic research and scientific papers
Chemical and Enzymatic Oxidation of 2-Aryl-1,3-oxathiolanes: Mechanism of the Hepatic Flavin-Containing Monooxygenase
Cashman, John R.,Proudfoot, John,Ho, Yen-Kuang,Chin, Marian S.,Olsen, Leslie D.
, p. 4844 - 4852 (2007/10/02)
The reaction of NaIO4, H2O2, and highly purified and microsomal hog and rat liver flavin-containing monooxygenase with 2-aryl-1,3-oxathiolanes was investigated.The ρ values determined from Hammett plots for the rate of S-oxygenation are consistent with substantial nucleophilic character for the chemical reaction but this does not preclude radical character in the reaction.For the biotransformation reactions, the data provide evidence for a minor role of cytochrome P-450 in the S-oxygenation of 2-aryl-1,3-oxathiolanes, but the flavin-containing monooxygenase represents by far the major pathway for S-oxide formation.The diastereochemical outcome of the S-oxygenation of 2-aryl-1,3-oxathiolanes was determined and, in general, hog liver flavin-containing monooxygenase demonstrated considerable S-oxygenation stereoselectivity while rat liver flavin-containing monooxygenase (FMO) was markedly less stereoselective.The presence of the minor cis S-oxide diastereomer in each case is due to incomplete diastereomeric processing by each enzyme (FMO and cytochrome P-450) and not to a competing, achiral nonenzymatic process. 2-Aryl-1,3-oxathiolane S-oxides are also oxygenated a second time by H2O2 or hog or rat liver microsomal and highly purified FMO.The immediate S,S-dioxygenated product is not stable and is rapidly converted to the corresponding benzaldehyde.That the chemical and enzymatic oxygenation of 2-aryl-1,3-oxathiolane S-oxides is much slower than its corresponding sulfide is quite apparent from the large dependence on the nature of the para substituent.The reactions of 2-aryl-1,3-oxathiolanes with H2O2 and FMO serve to demonstrate the electronic and stereochemical requirements for S-oxygenation of dialkyl sulfides and provide evidence that rat and hog liver FMO are two different forms of the same enzyme.
Fungal biotransformation of 1,3-oxathiolanes
Holland, Herbert L.,Munoz, Benito
, p. 2299 - 2303 (2007/10/02)
A series of 2,2-disubstituted 1,3-oxathiolanes has been incubated with fungi known to be capable of efficient asymmetric oxidation of sulfides to sulfoxides.In three cases (2-phenyl-1,3-oxathiolane, 2-methyl-2-phenyl-1,3-oxathiolane, and 2-tert-butyl-2-phenyl-1,3-oxathiolane), sulfoxidation occured to give a single diastereomer of sulfoxide, whose relative stereochemistry has been assigned by 1H nuclear magnetic resonance analysis.The sulfoxides were obtained as racemates or had low enantiomeric enrichment.In some cases ketones, assumed to be formed by spontaneous hydrolysis of oxathiolane sulfoxides, were obtained, together with their reduction products, secondary alcohols.
