Total synthesis of (+)-ampullicin and (+)-isoampullicin:: Two fungal metabolites with growth regulatory activity isolated from Ampulliferina sp 27

被引:21
作者
Bermejo, FA
Rico-Ferreira, R
Bamidele-Sanni, S
García-Granda, S
机构
[1] Univ Salamanca, Fac Ciencias Quim, Dept Quim Organ, E-37008 Salamanca, Spain
[2] Univ Oviedo, Fac Quim, Dept Quim Fis & Analit, Oviedo 3306, Spain
关键词
D O I
10.1021/jo010527+
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The total synthesis of the growth regulators (+)-ampullicin 1 and (+)-isoampullicin 2 from (R)(-)-carvone 5 was accomplished by application of an 18-step sequence with 4.5% overall yield. The crucial step of the synthetic strategy lies on the internal displacement of tosylate 13 by means of the lactone enolate. In this way, access was opened to the tricyclic core present in these biologically active sesquiterpenic amides. A Horner-Emmons reaction between the carbaldehyde 16 and the phosphonate 22 led us to the stereoselective preparation of (+)-ampullicin 1. Standard transformation of I into the thermodynamically more stable geometric isomer (+)-isoampullicin 2 was trivial. The absolute configuration of both amides was established by X-ray analysis of a sample of synthetic (+)-isoampullicin 2.
引用
收藏
页码:8287 / 8292
页数:6
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