海洋糖脂Erylusamine B四糖片段的合成研究  

Synthesis of tetrasaccharide fragment of marine glycolipid Erylusamine B

作　　者：李发荣 吕昌仑 曹爽 李春霞[1,2] LI Farong;LYU Changlun;CAO Shuang;LI Chunxia(Key Laboratory of Marine Drugs,Ministry of Education,Shandong Key Laboratory of Glycoscience and Glycotechnology,School of Medicine and Pharmacy,Ocean University of China,Qingdao 266003,China;Marine Biomedical Research Institute of Qingdao,Qingdao 266071,China)

机构地区：[1]中国海洋大学海洋药物教育部重点实验室,山东省糖科学与糖工程重点实验室,医药学院,山东青岛266003 [2]青岛海洋生物医药研究院,山东青岛266071

出　　处：《中国海洋药物》2024年第5期17-27,共11页Chinese Journal of Marine Drugs

基　　金：国家自然科学基金项目(U21A20297);山东省重点研发计划重大科技创新工程(2021ZDSYS22)资助。

摘　　要：目的 对海洋糖脂Erylusamine B的四糖片段进行合成研究,旨在为Erylusamine B的全合成及构效关系研究奠定基础。方法 以D-木糖为原料,通过7步反应以25.1%的产率制备了2-OH裸露的木糖受体6,经6步反应以55.3%的产率制备了4-OH裸露的木糖受体11;以全乙酰化的阿拉伯糖硫苷为原料,通过两步反应以87%的产率合成了三氯乙酰亚胺酯供体13,通过4步反应以59%的产率合成了硫苷供体16;供体13和木糖受体11进行糖苷化反应合成Ara-α-(1→4)-Xyl二糖17;硫苷供体16和木糖受体6经糖苷化反应合成Ara-α-(1→2)-Xyl二糖19;二糖供体17和二糖受体19经NIS/TMSOTf催化顺利合成四糖20。结果 通过[2+2]汇聚式合成策略以83%的糖苷化产率得到Ara-α-(1→4)-Xyl-β-(1→3)-[Ara-α-(1→2)]-Xyl四糖产物(20),为海洋糖脂Erylusamine B的合成提供物质基础和技术手段。Objective The tetrasaccharide fragment of marine glycolipid Erylusamine B was synthesized for the total synthesis of Erylusamine B and its biological activity in the future.Methods Xylose receptors 6 and 11 were synthesized from D-xylose with overall yields of 25.1% and 55.3%,respectively;arabinose trichloroacetimidate donor 13 and thiolglycoside donor 16 were synthesized from p-Tolyl-2,3,4-tri-O-acetyl-1-thio-α-L-arabinopyranoside 12 with 87% and 59% yields,respectively.Donor 13 was reacted with xylose acceptor 11 to afford the Ara-α-(1→4)-Xyl disaccharide 17.Thiolglycoside donor 16 coupled with xylose acceptor 6 to afford the Ara-α-(1→2)-Xyl disaccharide 19.Glycosylation of disaccharide donor 17 with acceptor 19 gave the tetrasaccharide fragment under the action of NIS and TMSOTf.Results Ara-α-(1→4)-Xyl-β-(1→3)-[Ara-α-(1→2)]-Xyl tetrasaccharide fragment 20 was obtained in 83% yield by a [2+2] convergent strategy,providing the material basis and technology for the synthesis of the marine glycolipid Erylusamine B.

关 键 词：糖脂 Erylusamine B 糖苷化 四糖 

分 类 号：R914[医药卫生—药物化学]