Isolation and structure elucidation of new radical oxidation products of 5-hydroxy steroids.
Three new products have been isolated from the lead-tetraacetate version of the hypoiodite oxidation of 3beta,17beta-diacetoxy-5-hydroxy-5 alpha-androstane. Along with the expected 1(10)-unsaturated 5,10-seco steroidal 5-ketones, the fragmentation reaction gave two epimeric C-4 iodides. Their structural assignment was based on X-ray data of one of them ((4R,10S)-4-iodo-3beta,17beta-diacetoxy-5,10-secoandrostan-5-one). The third new product was found to be the 5 beta,6 beta-epoxide resulting from the dehydration of the tertiary alcohol followed by epoxidation of the intermediate Delta(5)-olefin.
Khripach
Vladimir A
VA
Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich str., 5/2, 220141 Minsk, Belarus. khripach@iboch.bas-net.by
Zhabinskii
Vladimir N
VN
Kuchto
Anna I
AI
Zhiburtovich
Yuliya Y
YY
Lyakhov
Alexander S
AS
Govorova
Alla A
AA
Groen
Marinus B
MB
van der Louw
Jaap
J
de Groot
Aede
A
D002855:Chromatography, Thin Layer; D003460:Crystallization; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D012632:Secosteroids / Q000737:chemistry / Q000302:isolation & purification; D021241:Spectrometry, Mass, Electrospray Ionization; D013256:Steroids / Q000737:chemistry* / Q000302:isolation & purification*; D013329:Structure-Activity Relationship; D014961:X-Ray Diffraction
D012632:Secosteroids; D013256:Steroids