Premium
Reactivity of 5,10:8,14‐Disecosteroids: An unusual rearrangement of cyclodecene‐1,4‐dione systems to five‐membered‐ring spiro‐γ‐lactones
Author(s) -
Lorenc Ljubinka,
BondarenkoGheorghiu Lidija,
Krstić Natalija,
Fuhrer Hermann,
Kalvoda Jaroslav,
Mihailović Mihailo Lj.
Publication year - 1995
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19950780412
Subject(s) - chemistry , hydroxylation , intramolecular force , ring (chemistry) , stereochemistry , cleavage (geology) , reactivity (psychology) , androstane , bond cleavage , lactone , medicinal chemistry , organic chemistry , catalysis , alternative medicine , geotechnical engineering , pathology , fracture (geology) , engineering , enzyme , medicine
Upon heating in AcOH, the stereoisomeric ( Z )‐ and ( R )‐6,9‐dioxocyclodex‐3‐enyl derivatives, 5 and 6 , respectively, obtained by HgO/I 2 oxidation of 5‐hydroxy‐8‐oxo‐8,14‐seco‐5α‐androstane‐3β,17β‐diyl diacetate ( 3 ), undergo an unusual intramolecular rearrangement to give the corresponding unsaturated (5 R ,9 R )‐ and (5 R ,9 S )‐spiro‐lactones 7 and 8 , respectively. Hydroxylation of the CC bond in 7 and 8 , and subsequent glycol cleavage of the resulting diols 9 and 10 afforded the epimeric spiro‐lactones (5 R ,9 S )‐ 11 and (5 R ,9 R )‐ 14 , respectively, and in both cases, the ring‐D‐containing fragments 12 and 13 .