91739-70-7Relevant academic research and scientific papers
216. Bicyclooctanes. Syntheses and Hydrolyses of 6-exo-substituted 2-exo- and 2-endo-Bicyclooctyl p-Toluenesulfonates. Part 9
Grob, Cyril A.,Sawlewicz, Pawel
, p. 1859 - 1867 (1984)
The synthesis of the title compounds and their hydrolysis products in 70percent dioxane are described.
Orbital unsymmetrization of olefins arising from non-equivalent orbital interactions. σ-π Coupling in bicyclo[2.2.2]octenes
Ohwada, Tomohiko,Uchiyama, Masanobu,Tsuji, Motonori,Okamoto, Iwao,Shudo, Koichi
, p. 296 - 306 (2007/10/03)
We characterized experimentally the substituent effect of a 5-exo substituent on the π facial selectivities of bicyclo[2.2.2]octenes toward electrophilic oxidative reactions such as epoxidation and dihydroxylation, and we discuss the underlying orbital interactions of vicinal σ orbitals and the olefinic π orbital involved in bicyclo[2.2.2]octenes, and commonly in methylenenorbornanes. Of significance is the out-of-phase motif of these σ- π couplings. Electron-withdrawing substituents such as cyano and carboxylic acid groups unequalize the relevant σ-π coupling, leading to the observed syn-facial preference. Alkyl substituents exhibit an electron-donative perturbing effect, depending on the bicyclic ring system.
