Journal article

Publication year: 2001

Pages: 11248-11252

Journal: Journal of the American Chemical Society

Volume number: 123

Issue number: 45

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/ja0158096

Publisher: American Chemical Society

Abstract: 
The mechanisms of C-H and C-C bond activations with dimethyldioxirane (DMD) were studied experimentally and computationally at the B3LYP/6-311+G**//B3LYP/6-31G* density functional theory level for the propellanes 3,6-dehydrohomoadamantane (2) and 1,3-dehydroadamantane (3). The sigma (C-C) activation of 3 with DMD (DeltaG(double dagger) = 23.9 kcal mol(-1) and DeltaG(r) = -5.4 kcal mol(-1)) is the first example of a molecule-induced homolytic C-C bond cleavage. The C-H bond hydroxylation observed for 2 is highly exergonic (AG, = -74.4 kcal mol(-1)) and follows a concerted pathway (DeltaG(double dagger) = 34.8 kcal mol(-1)), in contrast to its endergonic molecule-induced homolysis (DeltaG(double dagger) = 28.8 kcal mol(-1) and DeltaG(r) = +9.2 kcal mol(-1)). The reactivities of 2 and 3 with CrO(2)Cl(2), which follow a molecule-induced homolytic activation mechanism, parallel the DMD results only for highly reactive 3, but differ considerably for more stable propellanes such as 4-phenyl-3,6-dehydrohomoadamantane (1) and 2.

Harvard Citation style: Fokin, A., Tkachenko, B., Korshunov, O., Gunchenko, P. and Schreiner, P. (2001) Molecule-induced alkane homolysis with dioxiranes, Journal of the American Chemical Society, 123(45), pp. 11248-11252. https://doi.org/10.1021/ja0158096

APA Citation style: Fokin, A., Tkachenko, B., Korshunov, O., Gunchenko, P., & Schreiner, P. (2001). Molecule-induced alkane homolysis with dioxiranes. Journal of the American Chemical Society. 123(45), 11248-11252. https://doi.org/10.1021/ja0158096