516-85-8Relevant academic research and scientific papers
Doubly allylic hydroperoxide formed in the reaction between sterol 5,7-dienes and singlet oxygen.
Albro,Corbett,Schroeder
, p. 310 - 315 (1994)
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.
Concise Synthesis of 9,11-Secosteroids Pinnigorgiols B and e
Li, Xinghui,Zhang, Zeliang,Fan, Huafang,Miao, Yinlong,Tian, Hailong,Gu, Yucheng,Gui, Jinghan
, p. 4886 - 4890 (2021)
Pinnigorgiols B and E are 9,11-secosteroids with a unique tricyclic γ-diketone framework. Herein, we report the first synthesis of these natural products from inexpensive, commercially available ergosterol. This synthesis features a semipinacol rearrangem
Synthesis of 9,11-Secosteroids Pinnisterol E, Glaciasterol B, and 6-Keto-aplidiasterol B
Fan, Huafang,Gui, Jinghan,Li, Xinghui,Miao, Yinlong,Zhang, Mengqing
supporting information, p. 1684 - 1688 (2022/03/14)
A 10-step gram-scale synthesis of 9,11-secosteroid pinnisterol E from the inexpensive ergosterol is reported. This synthesis features a series of highly selective redox transformations such as regioselective olefin hydrogenation (PtO2), acid-sensitive endoperoxide reduction (Al-Ni alloy, Zn), and regio- and diastereoselective dienone oxidation. The robustness of this strategy is clearly demonstrated through the formal synthesis of 11(9 → 7)abeo-steroid pleurocin B and the divergent synthesis of 9,11-secosteroids glaciasterol B and 6-keto-aplidiasterol B from the inexpensive cholesterol.
PRODUCTION AND PROPERTIES OF 1,4-CYCLIC ADDUCTS OF STEROID 5,7-DIENES WITH 3,6-PYRIDAZINEDIONE AND 1,4-PHTHALAZINEDIONE
Bogoslovskii, N. A.,Litvinova, G. E.,Titova, I. A.,Samokhvalov, G. I.,Mairanovskii, V. G.,et al.
, p. 1705 - 1710 (2007/10/02)
1,3-Phthalazinedione and 3,6-pyridazinedione, obtained by the action of lead tetraacetate or manganese dioxide on phthalohydrazide and of lead tetraacetate on malehydrazide, form 1,4-cyclic adducts in reaction with steroid 5,7-dienes; the reaction is promoted by the presence of aliphatic alcohols.The initial dienes can be regenerated from the synthesized cyclic adducts by reductive cleavage with complex metal hydrides or by electrochemical reduction.In addition to ergosterol, the action of a water-alcohol solution of alkali on the cyclic adduct of ergosterol with 1,4-phthalazinedione gives a salt-like compound, which is converted into 9(11)-dehydroergosterol and phthalohydrazide by the action of acids.
