CHEMICAL EVIDENCE FOR THE PARTICIPATION OF A PEREPOXIDE INTERMEDIATE IN THE REACTION OF SINGLET OXYGEN WITH MONO-OLEFINS IN RELATIONSHIP WITH THE BIOGENETIC PATHWAY TO HIGHLY OXIDIZED ABIETANE DITERPENES
Jg. Luis et al., CHEMICAL EVIDENCE FOR THE PARTICIPATION OF A PEREPOXIDE INTERMEDIATE IN THE REACTION OF SINGLET OXYGEN WITH MONO-OLEFINS IN RELATIONSHIP WITH THE BIOGENETIC PATHWAY TO HIGHLY OXIDIZED ABIETANE DITERPENES, Tetrahedron letters, 35(1), 1994, pp. 179-182
Chemical evidence has been obtained in two separate experiments for th
e participation of a perepoxide intermediate in the reaction of single
t oxygen with mono-olefins. The intramolecular trapping of such an int
ermediate in the reaction of 6,7-didehydrocarnosic acid derivatives wi
th molecular oxygen in unequivocal singlet oxygen-generating condition
s to give rosmanol and isorosmanol derivatives represents conclusive p
roof for the cited mechanism. Futhermore, such chemical evidence suppo
rts our earlier hypothesis of a biogenetic pathway to highly oxidized
abietatriene diterpenes in which enzymatic dehydrogenation and singlet
-state oxygen appear to play important roles.