Stereoselective sulfoxidation

Keywords sulfoxides, /refera-Diels-Alder reaction, stereoselectivity, sulfoxide mediator... 

H. Nagai, S. Matsumura, and K. Toshima, A novel promoter, heteropoly acid, mediated chemo- and stereoselective sulfoxide glycosidation reactions, Tetrahedron Lett., 41 (2000) 10233-10237. 

Hamman MA, Haehner-Daniels BD, Wrighton SA, et al. Stereoselective sulfoxidation of sulin-dac sulfide by flavin-containing monooxygenases. Comparison of human liver and kidney microsomes and mammalian enzymes. Biochem Pharmacol 2000 60(1) 7-17. 

The haem peroxidases are a superfamily of enzymes which oxidise a broad range of structurally diverse substrates by using hydroperoxides as oxidants. For example, chloroperoxidase catalyses the regioselective and stereoselective haloge-nation of glycals, the enantioselective epoxidation of distributed alkenes and the stereoselective sulfoxidation of prochiral thioethers by racemic arylethyl hydroperoxides [62]. The latter reaction ends in (i )-sulfoxides, (S)-hydroperoxides and the corresponding (R)-alcohol, all In optically active forms. 

Figure 6 Stereoselective sulfoxidation of 2-aryl-l,3-oxathiolanes by hog liver flavine-containing monooxygenase (FMO) and cytochrome P450-IIB1. (Taken from Cashman et al 1990.)...

Hydrocarbon monooxygenase from Pseudomonas oleovorans[7, 8> 12] also catalyzes the stereoselective sulfoxidation of methyl thioether substrates[131 with up to 80 % ee. The products obtained with this enzyme are probably of the R-configiration. 

Buronfosse, T, Moroni, R, Benoit, E., and Riviere, J. L. (1995), Stereoselective sulfoxidation of the pesticide methiocarb by flavin-containing monooxygenase and cytochrome P450-dependent monooxygenases of rat liver microsomes. Anticholinesterase activity of the two sulfoxide enantiomer. J. Biochem. Toxicol. 10, 179-189. 

In redox reactions, isolated oxidative enzymes such as laccase C from Trametes and horseradish/soybean peroxidases (with mediators) have been shown to possess good catalytic activity in common ILs on syringaldizine and veratryl alcohol, respectively [35]. Recently, oxidase-peroxidase-catalyzed chemo- and stereoselective sulfoxidations of thioanisole and methyl-2-naphthyl sulfide have been successfully carried out with a system of Coprinus cinereus (CiP) peroxidase and Aspergillus niger glucose oxidase (GOD) in 10% water in [BMIM][PF6] (Scheme 2). An enantiomeric... 

The first chiral zirconium(IV) catalyst for stereoselective sulfoxidation has also been reported (141). 

Arene.. dioxygenases catalyze reactions other than dihydroxylation of aromatics. For example, toluene dioxygenase catalyzes monooxygenation of indene and indan to 1-indenol and 1-indanol, respectively [382], oxidation of polyhalogenated compounds such as trichloroethylene [eq. (24)] [363, 388-390], and stereoselective sulfoxidation of sulfides [391, 392]. 

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