Journal article

The protoadamantane radical cation


Authors list: Fokin, AA; Tkachenko, BA; Shubina, TE; Gunchenko, PA; Gusev, DV; Vohs, JK; Robinson, GH; Yurchenko, AG; Schreiner, PR

Publication year: 2002

Pages: 3844-3849

Journal: European Journal of Organic Chemistry

Volume number: 2002

Issue number: 22

ISSN: 1434-193X

Publisher: Wiley


Abstract: 
DFT (B3LYP) and MP2 computations with a 6-31G* basis set show that a unique protoadamantane radical cation (1(.+)) structure with an elongated, half-broken C(6)-H bond prevails both in the gas phase and in solution. This is in agreement with the observed regioselectivity of the single electrontransfer oxidation of protoadamantane (1) with photoexcited 1,2,4,5-tetracyanobenzene, which only gives 5-(6-protoadamantyl)-1,2,4-tricyanobenzene (5), for which the X-ray crystal structure is reported. The regioselectivities for the functionalizations of 1 with electrophiles support this oxidation pathway. The H-coupled electron-transfer mechanism recently proposed for the C-H activation of alkanes with electrophilic oxidizers explains the high C(6) positional selectivities in the functionalization of 1 in electrophilic media.



Citation Styles

Harvard Citation style: Fokin, A., Tkachenko, B., Shubina, T., Gunchenko, P., Gusev, D., Vohs, J., et al. (2002) The protoadamantane radical cation, European Journal of Organic Chemistry, 2002(22), pp. 3844-3849. https://doi.org/10.1002/1099-0690(200211)2002:22<3844::AID-EJOC3844>3.0.CO;2-C

APA Citation style: Fokin, A., Tkachenko, B., Shubina, T., Gunchenko, P., Gusev, D., Vohs, J., Robinson, G., Yurchenko, A., & Schreiner, P. (2002). The protoadamantane radical cation. European Journal of Organic Chemistry. 2002(22), 3844-3849. https://doi.org/10.1002/1099-0690(200211)2002:22<3844::AID-EJOC3844>3.0.CO;2-C

Last updated on 2025-21-05 at 13:32