5α,11-二羟基-2-氧代桉烷-3-烯的全合成  

Total Synthesis of 5α-Hydroxy-isopterocarpolone

作　　者：关玉昆[1] 李平[2] 周罡[3] 高晓蕾[3] 李裕林[3] 

机构地区：[1]烟台大学药学院,烟台264005 [2]河南科技大学化工与制药学院,洛阳471003 [3]兰州大学功能有机分子化学国家重点实验室有机化学研究所,兰州730000

出　　处：《高等学校化学学报》2005年第7期1281-1283,M010,共4页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:20272021)资助

摘　　要：The first total synthesis of （+）-5α-hydroxy-isopterocarpolone （1）, an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from （+）-dihydrocarvone（2） was described. Compound 4 was stereoselectively prepared from compound 2 in three steps according to reference-. The treatment of tosylhydrazone 5, which was formed via the reaction of compound 4 and TsNHNH2 catalyzed by BF3-5Et2O, with an excess of n-butyllithium gave triene 6. Oxidation of triene 6 with singlet oxygen afforded the desired endo-peroxide 7 as a single product. Reductive cleavage of peroxide 7 with K2CO3 gave α-rotunol 3, a natural eudesmane firstly isolated in 1969. Hydrolysis of α-rotunol 3 with 10% sulfuric acid afforded （+）-5α-hydroxy-isopterocarpolone （1）. The structures of all the compounds were confirmed by IR, MS and NMR spectra.The first total synthesis of (+)-5α-hydroxy-isopterocarpolone (1), an oxygenated eudesmane isolated from Chinese folk medicine Artemisia eriopoda, starting from (+)-dihydrocarvone(2) was described. Compound 4 was stereoselectively prepared from compound 2 in three steps according to reference-. The treatment of tosylhydrazone 5, which was formed via the reaction of compound 4 and TsNHNH_2 catalyzed by BF_3-5Et_2O, with an excess of n-butyllithium gave triene 6. Oxidation of triene 6 with singlet oxygen afforded the desired endo-peroxide 7 as a single product. Reductive cleavage of peroxide 7 with K_2CO_3 gave α-rotunol 3, a natural eudesmane firstly isolated in 1969. Hydrolysis of α-rotunol 3 with 10% sulfuric acid afforded (+)-5α-hydroxy-isopterocarpolone (1). The structures of all the compounds were confirmed by IR, MS and NMR spectra.

关 键 词：桉烷 5α 11-二羟基-2-氧代桉烷-3-烯 全合成 倍半萜 

分 类 号：O621.3[理学—有机化学]