Stereoselective synthesis of 8,12-furanoeudesmanes from santonin. Absolute stereochemistry of natural furanoeudesma-1,3-diene and tubipofurane

被引:23
作者
Blay, G [1 ]
Cardona, L [1 ]
Garcia, B [1 ]
Pedro, JR [1 ]
Sanchez, JJ [1 ]
机构
[1] UNIV VALENCIA,FAC QUIM,DEPT QUIM ORGAN,E-46100 BURJASSOT,VALENCIA,SPAIN
关键词
D O I
10.1021/jo9521458
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Ketobutenolide 3, easily obtained from santonin (1), has been transformed into two natural furanoeudesmanes 4 and 5, isolated from Commiphora molmol and Tubipora musica, respectively. trans- And cis-decalin systems were obtained by stereoselective reduction of the C-4-C-5 double bond in 3 in the following way: hydrogenation of 3 over Pd/C followed by acidic treatment gave the cis isomer 10 as the major product; selective hydrogenation of the C-1-C-2 double bond with the Wilkinson's catalyst followed by reduction with NaTeH yielded mainly the trans isomer 9. Compounds 9 and 10 were transformed into 4 and 5 in parallel sequences. Optical rotation and CD measurements of the synthetic products revealed that the stereochemistry of both natural products should be revised to their enantiomeric form.
引用
收藏
页码:3815 / 3819
页数:5
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