Synthesis and catalytic properties in olefin epoxidation of chiral oxazoline dioxomolybdenum(VI) complexes
authors Bruno, SM; Monteiro, B; Balula, MS; Pedro, FM; Abrantes, M; Valente, AA; Pillinger, M; Ribeiro-Claro, P; Kuhn, FE; Goncalves, IS
nationality International
journal JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
author keywords molybdenum; oxide complexes; chiral ligands; oxazoline; epoxidation; mesoporous materials
keywords ASYMMETRIC CATALYSIS; ENANTIOSELECTIVE EPOXIDATION; ORGANOMOLYBDENUM(VI) OXIDES; CRYSTAL-STRUCTURES; ALLYLIC ALCOHOLS; DIOXO COMPLEXES; OXO COMPLEXES; VI COMPLEXES; MO-VI; MOLYBDENUM(VI)
abstract Dioxomolybdenum(VI) complexes with the general formula [MoO2X2 (N,N)] (X = Cl, OSiPh3) containing a chiral bidentate oxazoline ligand (N,N = 2,2'-bis [(4S)-4-benzyl-2-oxazoline]) have been prepared and characterised by H-1 NMR, IR spectroscopy and thermogravimetric analysis. The bis(chloro) complex was heterogenised in the ordered mesoporous silica MCM-41 by direct grafting in dichloromethane. Elemental analysis and Si-29 MAS NMR spectroscopy of the derivatised material indicated the presence of monopodally anchored species of the type O-2[(-O)(3)SiO]Cl(N,N). The complex [MoO2Cl2(N,N)] and the derivatised material exhibited initial activities of 147 and 255 mol mol(Mo)(-1) h(-1), respectively, in the catalytic epoxidation of cyclooctene using tert-butylhydroperoxide (tBuOOH) as the oxidant, both yielding 1,2-epoxycyclooctane quantitatively within 24 h at 55 degrees C. The MCM-41 grafted catalyst could be recycled with no loss in performance with respect to the epoxide yields obtained for reaction times above 2 h. With trans-p-methylstyrene as the substrate, the bis(chloro) complex and the derivatised material gave epoxides as the only products with yields in the range of 56-64% after 24 h, but no catalytic asymmetric induction was observed. The triphenylsiloxy complex was more active than the bis(chloro) complex for the epoxidation of trans-beta-methylstyrene, but the enantionteric excess was negligible and the corresponding diols were also formed. For the reaction catalysed by the supported material, changing the oxidant from tBuOOH to cumene hydroperoxide greatly improved the catalytic activity but the enantiomeric excess continued very low and the corresponding diol was the main product. (c) 2006 Elsevier B.V. All rights reserved.
publisher ELSEVIER SCIENCE BV
issn 1381-1169
year published 2006
volume 260
issue 1-2
beginning page 11
ending page 18
digital object identifier (doi) 10.1016/j.molcata.2006.06.049
web of science category Chemistry, Physical
subject category Chemistry
unique article identifier WOS:000242327500003

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