149404-85-3Relevant articles and documents
On the hydroxylation of bicyclo[2.1.0]pentane using dioxiranes
Curci, Ruggero,D'Accolti, Lucia,Fusco, Caterina
, p. 7087 - 7090 (2001)
The oxidation of bicyclo[2.1.0]pentane by isolated dimethyldioxirane and by the more powerful methyl(trifluoromethyl)dioxirane, affords selectively, the corresponding endo-2 alcohol along with the 2,3-diol in high yield, and no rearrangement products; this suggests that a concerted O-insertion mechanism should be preferred over radical pathways.
Timing of the Radical Recombination Step in Cytochrome P-450 Catalysis with Ring-Strained Probes
Montellano, Paul R. Ortiz de,Stearns, Ralph A.
, p. 3415 - 3420 (2007/10/02)
Notricyclane, methylcyclopropane, and bicyclopentane have been used to probe the catalytic mechanism of microsomal cytochrome P-450.Nortricyclane is oxidized by rat liver microsomes to nortricyclanol without the detectable formation of norborn-5-en-2-ol.Methylcyclopropane is similarly oxidized to cyclopropylmethanol without the detectable formation of 3-buten-1-ol or cyclobutanol.The radical pair in the hydroxylation reaction therefore collapses faster than the cyclopropylmethyl radical rearranges (1 x 108 s-1).In contrast, microsomal oxidation of bicyclopentane yields approximately a 7:1 mixture of endo-2-hydroxybicyclopentane and 3-cyclopenten-1-ol.Deuterium labeling studies indicate the endo hydrogen is predominantly or exclusively removed from, and the hydroxyl group is delivered to, the endo face in both the rearranged and unrearranged products.The results indicate that a radical pair is formed in P-450-catalyzed hydroxylations that collapses with stereochemical specificity at a rate in excess of 1 x 109 s-1.
