title: Structural factors for the formation of propellane-type products in the solvolysis of bicyclic bridgehead compounds
abstract: Methanolyses of 2-oxobicyclo[3.3.1]non-1-yl triflate, 3, 3-dimethyl-2-oxobicyclo[3.3.1]non-1-yl triflate, and 2-oxobicyclo[4. 3.1]dec-1-yl mesylate gave the corresponding propellanone in 12%, 20%, or 3.2% yield, respectively, beside substitution or rearranged products under typical conditions. No propellane-type product was obtained in the solvolyses of 1-bromobicyclo[3.3.1]nonane, 2-methylidenebicyclo[3.3.1]non-1-yl heptafluorobutyrate, and 3, 3-dimethyl-2-thioxobicyclo[3.3.1]non-1-yl tosylate. The factors that permit the formation of the propellane-type product from the intermediate bridgehead cations are examined with the aid of theoretical calculations at PM3 and B3LYP/6-31G.
authors.affiliation: Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan.
authors.initials: K
authors.lastname: Tokunaga
authors.initials: S
authors.lastname: Tachibana
authors.initials: T
authors.lastname: Okazaki
authors.initials: Y
authors.lastname: Ohga
authors.initials: T
authors.lastname: Kitagawa
authors.initials: K
authors.lastname: Takeuchi