Total Synthesis of Marine Glycosphingolipid Vesparioside B
Total Synthesis of Marine Glycosphingolipid Vesparioside B
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海洋鞘糖脂Vesparioside B的全合成
DOI：
10.1021/jacs.5b12589
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发表时间：
2016-02-10
影响因子：
15
通讯作者：
Yang, Jin-Song
中科院分区：
文献类型：
--
作者：
Gao, Peng-Cheng;Zhu, San-Yong;Yang, Jin-Song
海洋糖脂 vesparioside B（方案 1, 1，R-1 = n-C22H45）R-2 = n-C14H29）主要成分的首次全合成是通过收敛 [4 + 3] 偶联策略完成的。关键步骤包括立体选择性安装一组具有挑战性的 1,2-顺式糖苷键。分别开发了2-喹啉羰基辅助的α-半乳糖基化和新型β-阿拉伯糖基化，以合成α-呋喃半乳糖苷和β-阿拉伯吡喃糖苷键。此外，4,6-O-亚苄基控制的α-吡喃半乳糖基化反应使得左侧四糖供体2与右侧二糖脂质受体3有效连接，从而导致1的全合成。
The first total synthesis of a major component of marine glycolipid vesparioside B (Scheme 1, 1, R-1 = n-C22H45) R-2 = n-C14H29) has been accomplished through a convergent [4 + 3] coupling strategy. Key steps included stereoselective installment of a set of challenging 1,2-cis-glycoside bonds. A 2-quinolinecarbonyl-assisted alpha-galactosylation and a novel beta-arabinosylation were developed, respectively, to synthesize the alpha-galactofuranosidic and the beta-arabinopyranosidic linkages. Furthermore, a 4,6-O-benzylidene-controlled alpha-galactopyranosylation reaction allowed the efficient connection of the left tetrasaccharide donor 2 with the right disaccharide lipid acceptor 3, hence leading to the total synthesis of 1.