SPONGIAN PENTACYCLIC DITERPENES - STEREOSELECTIVE SYNTHESIS OF (-)-DENDRILLOL-1

被引:25
作者
ABAD, A
ARNO, M
CUNAT, AC
MARIN, ML
ZARAGOZA, RJ
机构
[1] Departamento de Química Orgánica, Universidad de Valencia, Valencia, Dr. Moliner 50
关键词
D O I
10.1021/jo00051a035
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A formal total synthesis of the spongian diterpene (-)-dendrillol-1 (3), through a consice approach that could be used for the synthesis of other pentacyclic spongian diterpenes, is reported. The synthesis is based on the intramolecular acetalization of an acid-dialdehyde 4, which is prepared from (+)-podocarp-8(14)-en-13-one (5) via a sequence of transformations involving (a) introduction of a latent dialdehyde unit on 5 by photochemical reaction with acetylene, (b) reductive carboxylation at C-13 of photoadduct 6 to obtain acid 18, and (c) elaboration of the dialdehyde moiety at C-8 and C-14 of 18 by ozonolysis. Several procedures that have been examined for the reductive carboxylation at C-13 of 6 are described. A simple three-step procedure to effect the conversion of a podocarp-8-en-13-one system into a C-17-functionalized beyerane compound is also reported.
引用
收藏
页码:6861 / 6869
页数:9
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