81386-79-0Relevant academic research and scientific papers
Regioselectivity on electroreductive transannular reaction of 7-methylenebicyclo[3.3.1]nonan-3-one
Itoh,Kato,Unoura,Senda
, p. 339 - 345 (2001)
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.
