REACTIVITY OF 5,10-8,14-DISECOSTEROIDS - AN UNUSUAL REARRANGEMENT OF CYCLODECENE-1,4-DIONE SYSTEMS TO 5-MEMBERED-RING SPIRO-GAMMA-LACTONES

被引：5

作者：

LORENC, L

BONDARENKOGHEORGHIU, L

KRSTIC, N

FUHRER, H

KALVODA, J

MIHAILOVIC, ML

机构：

[1] UNIV BELGRADE, FAC CHEM, YU-11001 BELGRADE, YUGOSLAVIA

[2] INST CHEM TECHNOL & MET, YU-11001 BELGRADE, YUGOSLAVIA

[3] CIBA GEIGY LTD, RES SERV, CH-4002 BASEL, SWITZERLAND

[4] CIBA GEIGY LTD, DIV PHARMACEUT, CH-4002 BASEL, SWITZERLAND

来源：

HELVETICA CHIMICA ACTA | 1995年 / 78卷 / 04期

关键词：

D O I：

10.1002/hlca.19950780412

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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-5 alpha-androstane-3 beta,17 beta-diyl diacetate (3), undergo an unusual intramolecular rearrangement to give the corresponding unsaturated (5R,9R)- and (5R,9S)-spiro-lactones 7 and 8, respectively. Hydroxylation of the C=C bond in 7 and 8, and subsequent glycol cleavage of the resulting diols 9 and 10 afforded the epimeric spiro-lactones (5R,9S)-11 and (5R,9R)-14, respectively,and in both cases, the ring-D-containing fragments 12 and 13.

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页码：891 / 898

页数：8

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