50763-63-8Relevant articles and documents
The Rearrangement of Allylic Hydroperoxides Derived from (+)-Valencene
Davies, Alwyn G.,Davison, Ian G. E.
, p. 825 - 830 (2007/10/02)
(+)-Valencene (I) reacts with triplet oxygen to give 84 percent of the secondary β-hydroperoxyde (II) and 15 percent of the α-hydroperoxide (III); reaction with singlet oxygen gives principally (ca. 80 percent) the tertiary β-hydroperoxide (IV).This undergoes a Schenck rearrangement to give suprafacially the β-hydroperoxide (II) by a non-dissociative mechanism which does not involve exchange of oxygen in an atmosphere of 18O2.The hydroperoxide (II) then undergoes a slower Smith epimerization to the α-hydroperoxide (III) by a dissociative mechanism which involves a substantial (> 55 percent) exchange.