由4-戊炔酸和5-己炔酸合成Muricatacin和6-乙酰氧基十六碳烷酸-5-内酯立体异构体有机化学.pdfVIP

DOI: 10.6023/cjoc201408035 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 由4-戊炔酸和5-己炔酸合成Muricatacin 和6-乙酰氧基十六碳烷酸-5- 内酯立体异构体 董宏波 杨明艳 张晓腾 王明安* ( 中国农业大学应用化学系 北京 100193) 摘要 以4-戊炔酸和 5- 己炔酸为原料, Sharpless 不对称双羟基化反应为关键步骤, 分别以 6～7 步反应及 33.5%～54.6% 的总收率合成了 muricatacin 和 6-乙酰氧基十六碳烷酸-5- 内酯的四个立体异构体. 它们的化学结构得到 1H NMR, 13C NMR, HR-ESI-MS 和 X 射线衍射的表征, (－)-epi-muricatacin 的绝对构型通过X 射线衍射予以证实. 关键词 muricatacin; 6- 乙酰氧基十六碳烷酸-5- 内酯; Sharpless 不对称双羟基化; 合成 Synthesis of Muricatacin and 6-Acetoxy-5-hexadecanolide Isomers from Pent-4-ynoic Acid and Hex-5-ynoic Acid Dong, Hongbo Yang, Mingyan Zhang, Xiaoteng Wang, Mingan* (Department of Applied Chemistry , China Agricultural University, Beijing 100193) Abstract The four isomers of 6-acetoxy-5-hexadecanolide and muricatacin were synthesized in 6～7 steps through pent- 4-ynoic acid and hex-5-ynoic acid as raw materials and Sharpless asymmetric dihydroxylation as the key step in overall yields of 33.5%～54.6%. Their structures were confirmed by 1H NMR, 13C NMR, HR-ESI-MS data and X-ray diffraction. The abso- lute configuration of ( －)-epi-muricatacin was also ascertained by X-ray diffraction analysis. Keywords muricatacin; 6-acetoxy-5-hexadecanolide; sharpless asymmetric dihydroxylation; synthesis [1] tigans) 的卵块表面分泌物中分离出的具有产卵引诱信息 Muricatacin 是 McLaughlin 等 首次从番荔枝科植 物刺果番荔枝(Annona Muricata) 的种子中分离到的天然 素功能的天然产物, Itsuo 等[5]确定了该引诱信息素的绝 产物, 并鉴定其是(4R,5R)和(4S,5S)-Muricatacin 光学异 对构型, 经研究发