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Volumn 131, Issue 20, 2009, Pages 6997-7004

Hydrogen-bond-assisted epoxidation of homoallylic and allylic alcohols with hydrogen peroxide catalyzed by selenium-containing dinuclear peroxotungstate

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLIC ALCOHOL; CATALYTIC ACTIVITY; COMPOUND I; COMPUTATIONAL COMPARISONS; COMPUTATIONAL STUDIES; DINUCLEAR; ELEMENTAL ANALYSIS; EPOXY ALCOHOLS; HETEROATOMS; HIGH REACTIVITY; HIGH YIELD; HYDROGEN BONDINGS; LEWIS ACIDITY; OXYGEN TRANSFER; PEROXOTUNGSTATES; TRANSITION-STATE; TUNGSTEN COMPLEX; TUNGSTEN SPECIES; TURNOVER FREQUENCY;

EID: 70149084747     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja901289r     Document Type: Article
Times cited : (93)

References (148)
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    • For the catalytic epoxidation by the do-transition metal catalysts, the oxidation states of the metal centers are not changed during the catalysis. The metal centers function as Lewis acids by withdrawing electrons from the O-O bond and thus increasing the electrophilic character of the coordinated peroxide. Active catalysts are the metal centers with strong Lewis acidity, (a) Thiel, W. R.; Eppinger, J Chem - Eur. J. 1997, 3, 696.
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    • note
    • 18c,23g
  • 78
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    • note
    • The epoxidation of 3-methyl-3-butenyl acetate gave the corresponding epoxide in 13% yield under the same reaction conditions as those in Table 1. The yield for the acetate derivative was much lower than that (84%) for the homoallylic alcohol la, suggesting that the hydroxyl functionality plays an important role in the present epoxidation.
  • 79
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    • note
    • 2 at 233 K showed a broad signal of the OH hydrogen at 1.91 ppm. Upon addition of one equivalent I (33 mM) with respect to la at 233 K, the broad signal was observed at 2.03 ppm. The downfield shift of la in the presence of I indicates the hydrogen bonding between I and la since the downfield shift of the OH hydrogen by the presence of the hydrogen bonding has been reported.
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    • The electron-withdrawing substituents decrease the electron density of the C=C double bond and reduce the π(C=C) HOMO energy, resulting in the decrease of the reactivity of the olefin with electrophilic oxidants.
    • The electron-withdrawing substituents decrease the electron density of the C=C double bond and reduce the π(C=C) HOMO energy, resulting in the decrease of the reactivity of the olefin with electrophilic oxidants.
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    • note
    • -1) (Figures S3-S5 and Tables S2-S5).
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    • 2.
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    • note
    • Cyclooctene was used as a model substrate to estimate the true oxygen transfer ability of the peroxotungstates without the hydrogen-bonding interaction between substrate and catalyst.
  • 99
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    • note
    • 35.36
  • 107
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    • In the case of the present peroxotungstates, the "inverse halogen dependence" found for mononuclear tungsten species was not observed, and the peroxotungstates with the electronically deshielded tungsten atoms snowed the high reactivity, (a) McFarlane, W.; Noble, A. M.; Wintfield, J. M. J. Chem. Soc. A 1971, 948.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.