Journalartikel

Jahr der Veröffentlichung: 1998

Seiten: 6494-6502

Zeitschrift: The Journal of Organic Chemistry

Bandnummer: 63

Heftnummer: 19

ISSN: 0022-3263

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

Verlag: 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-Zitierstil: 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-Zitierstil: 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