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

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  • Itoh Hiroki
    Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
  • Kato Ichiro
    Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
  • Unoura Kei
    Department of Material and Biological Chemistry, Faculty of Science, Yamagata University
  • Senda Yasuhisa
    Department of Material and Biological Chemistry, Faculty of Science, Yamagata University

書誌事項

公開日
2001
DOI
  • 10.1246/bcsj.74.339
  • 10.1002/chin.200126074
公開者
公益社団法人 日本化学会

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説明

A competitive transannular reaction occurred to give 7-methyltricyclo[3.3.1.03,7]nonan-3-ol (5) and 1-adamantanol (6) in the non-mediated electroreduction of 7-methylenebicyclo[3.3.1]nonan-3-one (1) in N,N-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 1•-, ΔΔH‡(5-exo - 6-endo) and ΔΔS‡(5-exo - 6-endo), were evaluated to be -3.1 kcal mol-1 and -11 cal mol-1 K-1, respectively. Semiempirical PM3 (RHF and UHF) calculations were also carried out to elucidate the reaction mechanism.

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