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Volumn 120, Issue 5, 1998, Pages 948-954

The mechanistic basis for electronic effects on enantioselectivity in the (salen)Mn(III)-catalyzed epoxidation reaction

Author keywords

[No Author keywords available]

Indexed keywords

MANGANESE;

EID: 0032506979     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973468j     Document Type: Article
Times cited : (399)

References (59)
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    • Ojima, I., Ed. VCH: New York; Chapter 4.2. Asymmetric aziridination:
    • (b) Jacobsen, E. N. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; Chapter 4.2. Asymmetric aziridination:
    • (1993) Catalytic Asymmetric Synthesis
    • Jacobsen, E.N.1
  • 10
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    • Ojima, I., Ed. VCH: New York; Chapter 3
    • Asymmetric cyclopropanation: Doyle, M. P. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; Chapter 3.
    • Catalytic Asymmetric Synthesis , pp. 1993
    • Doyle, M.P.1
  • 11
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    • Wilkinson, G., Stone, F. G. A., Abel, E. W., Hegedus, L. S., Eds. Pergamon: New York, Chapter 11.1
    • (a) Jacobsen, E. N. In Comprehensive Organometallic Chemistry II; Wilkinson, G., Stone, F. G. A., Abel, E. W., Hegedus, L. S., Eds.; Pergamon: New York, 1995; Vol. 12, Chapter 11.1.
    • (1995) Comprehensive Organometallic Chemistry II , vol.12
    • Jacobsen, E.N.1
  • 43
    • 0030052488 scopus 로고    scopus 로고
    • Katsuki has reported a case where a MeO-substituted chiral (salen)- Mn complex affords lower epoxidation enantioselectivity than the corresponding catalyst bearing a H-substituent: Hamada, T.; Fukuda, T.; Imanishi, H.; Katsuki, T. Tetrahedron 1996, 52, 515.
    • (1996) Tetrahedron , vol.52 , pp. 515
    • Hamada, T.1    Fukuda, T.2    Imanishi, H.3    Katsuki, T.4
  • 44
    • 0030804770 scopus 로고    scopus 로고
    • For recent efforts directed toward the isolation of reactive Mn(V) oxo complexes, see: (a) Groves, J. T.; Lee, J.; Marla, S. S. J. Am. Chem. Soc. 1997, 119, 6269.
    • (1997) J. Am. Chem. Soc. , vol.119 , pp. 6269
    • Groves, J.T.1    Lee, J.2    Marla, S.S.3
  • 47
    • 0030874375 scopus 로고    scopus 로고
    • Katsuki has demonstrated recently that sparteine can induce moderate enantioselectivity in the epoxidation of certain olefins catalyzed by achiral (salen)Mn complexes and has proposed a mechanism involving complexation of the amine to the catalyst resulting in a nonplanar reactive ligand conformation: Hashihayata, T.; Ito, Y.; Katsuki, T. Tetrahedron 1997, 53, 9541. However, the very low yields of epoxide obtained in these reactions (0.1-0.5 equiv relative to sparteine) raise the possibility that any enantioselectivity might be due instead to secondary reactions such as kinetic resolution of epoxide mediated by the chiral amine. This notion is supported by the fact that epoxide yields decrease and enantioselectivities increase with added amine or with added water in the presence of amine.
    • (1997) Tetrahedron , vol.53 , pp. 9541
    • Hashihayata, T.1    Ito, Y.2    Katsuki, T.3
  • 49
    • 80355142408 scopus 로고    scopus 로고
    • The most direct test of this hypothesissdirect comparison of the rates of reactions catalyzed by electron-rich and elctron-poor catalystssis precluded by the fact that mass transport of the aqueous oxidant into the organic layer is the rate-limiting step under biphasic conditions: Suárez, A.; Pospisil, P. J.; Jacobsen, E. N. Unpublished results
    • The most direct test of this hypothesissdirect comparison of the rates of reactions catalyzed by electron-rich and elctron-poor catalystssis precluded by the fact that mass transport of the aqueous oxidant into the organic layer is the rate-limiting step under biphasic conditions: Suárez, A.; Pospisil, P. J.; Jacobsen, E. N. Unpublished results.
  • 53
    • 0004105856 scopus 로고
    • 2nd ed.; John Wiley & Sons: New York
    • Isaacs, N. Physical Organic Chemistry, 2nd ed.; John Wiley & Sons: New York, 1995; pp 296-301.
    • (1995) Physical Organic Chemistry , pp. 296-301
    • Isaacs, N.1
  • 56
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    • 2nd ed.; John Wiley & Sons: New York
    • (a) Isaacs, N. Physical Organic Chemistry, 2nd ed.; John Wiley & Sons: New York, 1995; pp 116-7.
    • (1995) Physical Organic Chemistry , pp. 116-7
    • Isaacs, N.1


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