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Volumn 47, Issue 52, 2008, Pages 10195-10198

A μ-oxo-μ-η2:η2-peroxo titanium complex as a reservoir of active species in asymmetric epoxidation using hydrogen peroxide

Author keywords

Asymmetric catalysis; Epoxidation; Hydrogen peroxide; Peroxo ligands; Titanium

Indexed keywords

CATALYSIS; HYDROGEN; HYDROGEN PEROXIDE; LIGANDS; OXIDATION; TITANIUM;

EID: 57749116177     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200804685     Document Type: Article
Times cited : (64)

References (51)
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    • For recent examples of organocatalytic asymmetric epoxidation, see: a
    • For recent examples of organocatalytic asymmetric epoxidation, see: a) T. Ooi, D. Ohara, M. Tamura, K. Maruoka, J. Am. Chem. Soc. 2004, 126, 6844-6845;
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    • The subscript N represents the configuration at the nitrogen atoms.
    • The subscript "N" represents the configuration at the nitrogen atoms.
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    • If the stereochemistry of the nitrogen atoms is ignored, there are six possible isomers for the di-μ-oxo titanium complexes: V. I. Tararov, V. S. Larichev, M. A. Moscalenko, L. V. Yashkina, V. N. Khrustalev, M. Y. Antipin, A. Börner, Y. N. Belokon, Enantiomer 2000, 5, 169-173.
    • If the stereochemistry of the nitrogen atoms is ignored, there are six possible isomers for the di-μ-oxo titanium complexes: V. I. Tararov, V. S. Larichev, M. A. Moscalenko, L. V. Yashkina, V. N. Khrustalev, M. Y. Antipin, A. Börner, Y. N. Belokon, Enantiomer 2000, 5, 169-173.
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    • CCDC-696658 (2), 696659 (3), 697424 (4), and 696660 (5) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • CCDC-696658 (2), 696659 (3), 697424 (4), and 696660 (5) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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    • Unfortunately, we could not obtain a sufficient amount of complex 4 for the conversion-vs.-time experiment.
    • Unfortunately, we could not obtain a sufficient amount of complex 4 for the conversion-vs.-time experiment.
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    • We also detected an ion peak corresponding to a di-μ-peroxo species in the epoxidation of 1,2-dihydronaphthalene by LC/ESI-MS analysis.
    • We also detected an ion peak corresponding to a di-μ-peroxo species in the epoxidation of 1,2-dihydronaphthalene by LC/ESI-MS analysis.
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    • We have proposed that the corresponding di-μ-oxo titanium-(salalen) complex also gives a m-oxo-m-peroxo species in the reaction with hydrogen peroxide Ref, 4a
    • We have proposed that the corresponding di-μ-oxo titanium-(salalen) complex also gives a m-oxo-m-peroxo species in the reaction with hydrogen peroxide (Ref. [4a]).
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    • Although Talsi and Babushkin also reported the synthesis of a μ-oxo-μ-peroxo titanium complex bearing an acetylacetonato ligand using 95% hydrogen peroxide, the structure was not determined unambiguously: E. P. Talsi, D. E. Babushkin, J. Mol. Catal. A 1996, 106, 179-185
    • Although Talsi and Babushkin also reported the synthesis of a μ-oxo-μ-peroxo titanium complex bearing an acetylacetonato ligand using 95% hydrogen peroxide, the structure was not determined unambiguously: E. P. Talsi, D. E. Babushkin, J. Mol. Catal. A 1996, 106, 179-185.
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    • For μ-η2:η2-peroxo complexes of other metals, see: a
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    • We cannot rule out the possibility that complexes 3 and 4 are converted directly into an active species
    • We cannot rule out the possibility that complexes 3 and 4 are converted directly into an active species.


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