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Volumn 69, Issue 10, 2004, Pages 3431-3438

Aerobic Oxidation of Benzyl Alcohols Catalyzed by Aryl Substituted N-Hydroxyphthalimides. Possible Involvement of a Charge-Transfer Complex

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; BENZENE; CATALYSTS; CHARGE TRANSFER; COMPLEXATION; ENTHALPY; KETONES; OXIDATION; REACTION KINETICS; SUBSTITUTION REACTIONS;

EID: 2442517266     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049887y     Document Type: Article
Times cited : (101)

References (48)
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    • (1991) Dioxygen Activation and Homogeneous Catalytic Oxidation
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    • Dioxygen activation and homogeneous catalytic oxidation; Simandi, L. L., Ed.; Elsevier: Amsterdam, 1991. The activation of dioxygen and homogeneous catalytic oxidation; Barton, D. H. R., Martell, A. E., Sawyer, D. T., Eds.; Plenum: New York, 1993.
    • (1993) The Activation of Dioxygen and Homogeneous Catalytic Oxidation
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    • Highlet, L. J.; Wildman, W. C. J. Am. Chem. Soc. 1955, 77, 4399. Lee, D. G.; Spitzer, U. A. J. Org. Chem. 1970, 35, 3589. Stevens, R. V.; Chapman, K. T. ; Weller, H. N. J. Org. Chem. 1980, 45, 2030. Menger, F. M.; Lee, C. Tetrahedron Lett. 1981, 22, 1655.
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    • Highlet, L. J.; Wildman, W. C. J. Am. Chem. Soc. 1955, 77, 4399. Lee, D. G.; Spitzer, U. A. J. Org. Chem. 1970, 35, 3589. Stevens, R. V.; Chapman, K. T. ; Weller, H. N. J. Org. Chem. 1980, 45, 2030. Menger, F. M.; Lee, C. Tetrahedron Lett. 1981, 22, 1655.
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    • Highlet, L. J.; Wildman, W. C. J. Am. Chem. Soc. 1955, 77, 4399. Lee, D. G.; Spitzer, U. A. J. Org. Chem. 1970, 35, 3589. Stevens, R. V.; Chapman, K. T. ; Weller, H. N. J. Org. Chem. 1980, 45, 2030. Menger, F. M.; Lee, C. Tetrahedron Lett. 1981, 22, 1655.
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    • note
    • 3CN.
  • 22
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    • note
    • All the catalysts were completely soluble in AcOEtYdioxane 1:1 except for 1g which was thus not used. in the kinetic studies.
  • 23
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    • note
    • +) proposed by Arnold and his associates.19
  • 25
    • 2442590538 scopus 로고    scopus 로고
    • note
    • A ρ value (-0.69) very close to that here reported was determined by Minisci et al. for the aerobic oxidation of benzylic alcohols by the unsubstituted NHPI.10)
  • 27
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    • note
    • 23 an increase of the KIE should be expected by decreasing the O-H BDE of the aryl substituted NHPI, i.e., by introducing electron-donating substituents.
  • 29
    • 0344391968 scopus 로고    scopus 로고
    • Such a high isotope effect value was interpreted as due to quantum mechanical.tunneling taking part in the benzylic HAT from the alcohol to the PINO. Nobuyoshi, K.; Saha, B.; Espenson, J. H. J. Org. Chem. 2003, 68; 9364.
    • (2003) J. Org. Chem. , vol.68 , pp. 9364
    • Nobuyoshi, K.1    Saha, B.2    Espenson, J.H.3
  • 30
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    • note
    • Rate-determining hydrogen atom abstraction from C-H bonds by PINO (Scheme 1, path b) in aerobic oxidations catalyzed by NHPI is well documented.3,9-11 The possibility of a rate-determining formation of aryl-substituted PINO (Scheme 1, path d) should be considered if a higher alcohol/X-NHPI molar ratio is used.14.
  • 31
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    • note
    • 2 system.
  • 32
    • 2442425075 scopus 로고    scopus 로고
    • note
    • . + ρσ+) proposed by Arnold.TM
  • 36
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    • note
    • 2 groups could be also explained by an electron transfer mechanism from the alcohol to the X-PINO. We have excluded this possibility by the fact that the oxidation of the mechanistic probe 1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanol led to the formation of 1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanone as the only reaction product and no traces of 3,4-dimethoxybenzaldehyde have been detected (see the Experimental Section).30
  • 42
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    • (1981) J. Am. Chem. Soc. , vol.103 , pp. 7240
    • Fukuzumi, S.1    Kochi, J.K.2


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