Journal article

Publication year: 1998

Pages: 6494-6502

Journal: The Journal of Organic Chemistry

Volume number: 63

Issue number: 19

ISSN: 0022-3263

DOI Link: https://doi.org/10.1021/jo980402d

Publisher: American Chemical Society

Abstract: 
The structures and reaction mechanisms of some tricyclic compounds and propellanes were investigated computationally at the BLYP/6-311+G**//BLYP/G-31G* nonhybrid density functional level, in particular to elucidate the elementary steps of the single-electron transfer (SET) oxidation reactions observed experimentally in the presence of oxidizing electrophiles (e.g., NO2+BF4-). Adiabatic ionization potentials (IP), proton affinities (PA), and strain energies were evaluated, the last from the heats of formation derived from homodesmotic equations. The low IP's and high PA's of highly strained propellanes such as 3,6-dehydrohomoadamantane help rationalize the single electron-transfer reactions that occur with oxidizing electrophiles. Electrophiles need not attack regions of highest electron density (the propellanic bond); the radical cation intermediates are trapped by nucleophiles. SET must be considered as an important potential mechanism for the activation of strained aliphatic hydrocarbons.

Harvard Citation style: Fokin, A., Schreiner, P., von Ragué Schleyer, P. and Gunchenko, P. (1998) Electrophilic and oxidative activation of the central C-C bond in [3.3.n]propellanes: A theoretical study, The Journal of Organic Chemistry, 63(19), pp. 6494-6502. https://doi.org/10.1021/jo980402d

APA Citation style: Fokin, A., Schreiner, P., von Ragué Schleyer, P., & Gunchenko, P. (1998). Electrophilic and oxidative activation of the central C-C bond in [3.3.n]propellanes: A theoretical study. The Journal of Organic Chemistry. 63(19), 6494-6502. https://doi.org/10.1021/jo980402d