Doubly allylic hydroperoxide formed in the reaction between sterol 5,7-dienes and singlet oxygen
Albro, PW; Corbett, JT; Schroeder, JL
| HERO ID | 1399886 |
|---|---|
| In Press | No |
| Year | 1994 |
| Title | Doubly allylic hydroperoxide formed in the reaction between sterol 5,7-dienes and singlet oxygen |
| Authors | Albro, PW; Corbett, JT; Schroeder, JL |
| Journal | Photochemistry and Photobiology |
| Volume | 60 |
| Issue | 4 |
| Page Numbers | 310-315 |
| Abstract | Ergosterol and 7-dehydrocholesterol, common 5,7-conjugated diene sterols, react with photochemically produced singlet oxygen very efficiently to yield, in parallel pathways, the corresponding 5,8-endoperoxides and the 7 beta-hydroperoxy-5,8(9),22-trienol or -5,8(9)-dienol, respectively. The hydroperoxides decompose in an acid-catalyzed reaction to generate hydrogen peroxide and the 5,7,9(11),22-tetraenol or 5,7,9(11) trienol, respectively, with 1:1 stochiometry. The molar ratio of endoperoxide to hydroperoxide was constant (16:5) with two different reaction solvents, two different photosensitizers, and at all time points between 5 min and 3 h from the start of irradiation. Ergosterol did not react with either hydrogen peroxide or superoxide ion under our reaction conditions. Inhibition studies with nitrogen, 2,5-dimethylfuran, beta-carotene, and tert-butanol confirmed the involvement of singlet oxygen in these reactions. The unstable hydroperoxide would be expected to have undesirable biological consequences if formed in vivo. |
| Pmid | 7991659 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Language Text | English |