SarsolilideA的合成研究———十四元碳环骨架的构建.pdfVIP

2004 年第 62 卷 化 学 学 报 Vol. 62 , 2004 第 8 期 , 811～817 ACTA CHIMICA SINICA No. 8 , 811 ～817 Sarsolilide A 的合成研究———十四元碳环骨架的构建 段志勇　　张家仲　　许杏祥 ( 中国科学院上海有机化学研究所　上海 200032) 摘要 　在对目标分子 Sarsolilide A 的全合成研究工作中 ,从香叶醇和异丁醛出发 ,分别制备了醛前体 11 和磷酸酯前体 18 , 并以分子间 HWE 反应实现了两个前体的联接. 利用 Sharpless 不对称双羟化反应区域选择性地引入了化合物 20 中的7 ,8位 双羟基. 经多步转化制得关环前体 5 . 利用低价钛参与的 McMurry 反应实现了十四元西松烷碳环的闭合 ,从而完成了关键中 间体化合物23 的合成. 关键词 　Sarsolilide A , McMurry 大环化法 ,HWE 反应 ,Sharpless 不对称双羟化反应 ,全合成 Synthetic Studies of Sarsolilide A ——— Construction of the 14Membered Cembranoid Skeleton DUAN , ZhiYong 　　ZHANG, JiaZhong 　　XU , XingXiang ( Shanghai Institute of Organic Chemistry , Chinese Academy of Sciences , Shanghai 200032) Abstract 　In the total synthesis of Sarsolilide A as a target molecule , the precursors 11 and 18 , which were synthesized from geraniol and isobutyraldehyde respectively , were condensed via intermolecular HWE reaction. And the dihydroxyl groups at 7C and 8C in compound 20 were regioselectively introduced by Sharpless AD reaction. Subsequent conventional transformations afforded the cyclization precursor 5 . The construction of the 14membered cembranoid carbon ring was realized by low valent titanium induced McMurry reaction , giving compound 23 as the key intermediate. Keywords 　Sarsolilide A , McMurry coupling , HWE reaction , Sharpless asymmetric dihydroxylation , total synthesis