Full Paper

Sulfoxygenation Catalysed by Oxidovanadium Complexes

  1. Pingsong Wu,
  2. Cem Çelik,
  3. Gabriella Santoni,
  4. Jérome Dallery,
  5. Dieter Rehder

Article first published online: 17 OCT 2008

DOI: 10.1002/ejic.200800772

Issue

European Journal of Inorganic Chemistry

European Journal of Inorganic Chemistry

Volume 2008, Issue 33, pages 5203–5213, November 2008

Additional Information

How to Cite

Wu, P., Çelik, C., Santoni, G., Dallery, J. and Rehder, D. (2008), Sulfoxygenation Catalysed by Oxidovanadium Complexes. Eur. J. Inorg. Chem., 2008: 5203–5213. doi: 10.1002/ejic.200800772

Author Information

  1. Chemistry Department, University of Hamburg, 20146 Hamburg, Germany

Publication History

  1. Issue published online: 11 NOV 2008
  2. Article first published online: 17 OCT 2008
  3. Manuscript Received: 1 AUG 2008

Funded by

  • Deutsche Forschungsgemeinschaft (DFG). Grant Number: RE 431/20

SEARCH

SEARCH BY CITATION

ARTICLE TOOLS

View Full Article (HTML) Get PDF (577K)

Keywords:

  • Oxidovanadium complexes;
  • Ethanolamines;
  • Sulfoxygenation;
  • Models of peroxidases;
  • Vanadate-dependent peroxidase

Abstract

Model complexes of vanadate-dependent peroxidases, viz. oxidovanadium(V) complexes of the general composition [VO(Hn–xL)], have been prepared and characterised. HnL is an n-basic di- or trichiral aminodiethanol [HOCH(Ph)CH2]2NR, with R = N-methylimidazolyl (H2LA), tris(hydroxymethyl)methyl (H5LB, 2 isomers), 2,3-dihydroxypropyl (H4LC, 2 isomers) and 2-hydroxy-3-trityloxypropyl (H3LD). These ligands form the complexes [VO(OH)(LA)], [VO(H2LB)], trigonal-bipyramidal [VO(HLC)]tbp and octahedral Λ-[VO(HLC)]oct. The ligands R,R,S-H4LC and R,R,R-H3LD, and the complexes Λ-[VO(R,R,S-HLC)]oct and [VO(R,R,S-HLC)]tbp have been characterised by X-ray structure analysis. The complexes [VO(H2LB)] and [VO(HLC)] were immobilised on Merrifield and Barlos resin by anchoring through a free alcoholic group in the ligand side-chain R. {[VO(H2O)LE]}, an oxidovanadium(IV) complex tethered to Merrifield resin, was prepared by treating [VO(acac)2] with {HLE}, the immobilised Schiff base ligand obtained by condensation of salicylaldehyde with resin-anchored lysine. The complexes and in situ systems ([VO(OiPr)3] + ligand) as well as the immobilised complexes were investigated for their catalytic activity in the oxygenation, by cumyl hydroperoxide, of thioanisol to its sulfoxide. All of the systems were active, with a selectivity (sulfoxide vs. sulfone) of 95–98 %. Satisfactory turnover rates and a chiral induction up to 37 % ee were observed.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

View Full Article (HTML) Get PDF (577K)