Regioselectivity on Electroreductive Transannular Reaction of 7-Methylenebicyclo[3.3.1]nonan-3-one

Access this Article

Search this Article

Author(s)

Abstract

A competitive transannular reaction occurred to give 7-methyltricyclo[3.3.1.0<sup>3,7</sup>]nonan-3-ol (<b>5</b>) and 1-adamantanol (<b>6</b>) in the non-mediated electroreduction of 7-methylenebicyclo[3.3.1]nonan-3-one (<b>1</b>) in <i>N</i>,<i>N</i>-dimethylformamide. The apparent temperature dependence of the regioselectivity of the reaction may be attributed to the competitive operation of both kinetic and thermodynamic controls in the cyclization of the ketyl radical anion. The differences in the parameter of activation between the 5-exo- and 6-endocyclizations of <b>1</b><sup>•-</sup>, ΔΔ<i>H</i><sup>‡</sup><sub>(5-exo - 6-endo)</sub> and ΔΔ<i>S</i><sup>‡</sup><sub>(5-exo - 6-endo)</sub>, were evaluated to be -3.1 kcal mol<sup>-1</sup> and -11 cal mol<sup>-1</sup> K<sup>-1</sup>, respectively. Semiempirical PM3 (RHF and UHF) calculations were also carried out to elucidate the reaction mechanism.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 74(2), 339-345, 2001-02-15

    The Chemical Society of Japan

References:  20

  • <no title>

    SHONO T.

    Electron transfer processes in organic chemistry

    Cited by (1)

  • <no title>

    SHONO T.

    J. Am. Chem. Soc. 93, 5284, 1971

    Cited by (3)

  • <no title>

    SHONO T.

    J. Am. Chem. Soc. 100, 545, 1978

    Cited by (2)

  • <no title>

    SHONO T.

    J. Am. Chem. Soc. 108, 4676, 1986

    Cited by (2)

  • <no title>

    BALDWIN J. E.

    J. Chem. Soc. Chem. Comm. 1976, 734

    Cited by (2)

  • <no title>

    SENDA Y.

    J. Chem. Soc., Perkin Trans. 2 1981, 90

    Cited by (1)

  • <no title>

    ISHIYAMA J. -I

    Chem. Lett. 1983, 771

    Cited by (1)

  • <no title>

    GROB C. A.

    Helv. Chim. Acta 60, 1890, 1977

    Cited by (1)

  • <no title>

    MORI T.

    Tetrahedron, Lett. 1970, 2419

    Cited by (1)

  • <no title>

    MOMOSE T.

    Chem. Pharm. Bull 26, 288, 1978

    Cited by (1)

  • <no title>

    SCHAEFER J. P.

    J. Org. Chme. 32, 1372, 1967

    Cited by (1)

  • <no title>

    EAKIN M.

    J. Chem. Soc., Chem. Comm. 1965, 206

    Cited by (1)

  • <no title>

    POUCHERT C. J

    The Aldrich Library of NMR Spectra 1, 120C, 1974

    Cited by (1)

  • <no title>

    POUCHERT C. J

    The Aldrich Library of Infrared Spectra 86F, 1970

    Cited by (1)

  • <no title>

    CAChe MOPAC ver. 94

    Cited by (1)

  • <no title>

    STEWART J. J. P.

    J. Comput. Chem. 10, 209, 1989

    Cited by (66)

  • <no title>

    HIRANO T. ed

    Bunshikidoho MOPAC guide book, 1994

    Cited by (1)

  • <no title>

    SWARTZ J. E.

    J. Am. Chem. Soc. 111, 1211, 1989

    Cited by (3)

  • <no title>

    LOMBARDO F.

    J. Org. Chem. 56, 2422, 1991

    Cited by (2)

  • <no title>

    MUELLER A. M.

    J. Org. Chem. 63, 4581, 1998

    Cited by (1)

Codes

  • NII Article ID (NAID)
    10009158715
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    5684471
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
Page Top