caa a22 4500 475844254 CHVBK 20180406123909.0 cr unu---uuuuu 170329e20000801xx s 000 0 eng 10.1023/A:1009094619249 doi (NATIONALLICENCE)springer-10.1023/A:1009094619249 Vanadium-catalysed enantioselective sulfoxidations: rational design of biocatalytic and biomimetic systems [Elektronische Daten] [Fred van de Velde, Isabel Arends, Roger Sheldon] Approaches to the rational design of vanadium-based biocatalytic and biomimetic model systems as catalysts for enantioselective oxidations are reviewed. Incorporation of vanadate ion into the active site of phytase (E.C. 3.1.3.8), which in vivo mediates the hydrolysis of phosphate esters, afforded a relatively stable and inexpensive semi-synthetic peroxidase. It catalysed the enantioselective oxidation of prochiral sulfides with H2O2 affording the S-sulfoxide, e.g., in 68% ee at 100% conversion for thioanisole. Amongst the transition metal oxoanions that are known to be potent inhibitors of phosphatases, only vanadate resulted in a semi-synthetic peroxidase, when incorporated into phytase. In a biomimetic approach, vanadium complexes of chiral Schiff's base complexes were encapsulated in the super cages of a hydrophobic zeolite Y. Unfortunately, these ship-in-a-bottle complexes afforded only racemic sulfoxide in the catalytic oxidation of thioanisole with H2O2. Kluwer Academic Publishers, 2000 semi-synthetic vanadium peroxidases nationallicence enantioselective oxidation nationallicence vanadate phytase nationallicence vanadium complexes nationallicence van de Velde Fred Laboratory of Organic Chemistry and Catalysis, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands aut Arends Isabel Laboratory of Organic Chemistry and Catalysis, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands aut Sheldon Roger Laboratory of Organic Chemistry and Catalysis, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands aut Topics in Catalysis Kluwer Academic Publishers-Plenum Publishers 13/3(2000-08-01), 259-265 1022-5528 13:3<259 2000 13 11244 https://doi.org/10.1023/A:1009094619249 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1023/A:1009094619249 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- van de Velde Fred Laboratory of Organic Chemistry and Catalysis, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands aut NATIONALLICENCE 700 1- Arends Isabel Laboratory of Organic Chemistry and Catalysis, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands aut NATIONALLICENCE 700 1- Sheldon Roger Laboratory of Organic Chemistry and Catalysis, Delft University of Technology, Julianalaan 136, 2628 BL, Delft, The Netherlands aut NATIONALLICENCE 773 0- Topics in Catalysis Kluwer Academic Publishers-Plenum Publishers 13/3(2000-08-01), 259-265 1022-5528 13:3<259 2000 13 11244 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer