Solid-phase synthesis of core 3 and core 6 O-glycan-linked glycopeptides by benzyl-protection method
Solid-phase synthesis of core 3 and core 6 O-glycan-linked glycopeptides by benzyl-protection method
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DOI：
10.1016/j.tet.2006.12.087
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发表时间：
2007-03-05
期刊：
影响因子：
2.1
通讯作者：
Nakahara, Yoshiaki
中科院分区：
文献类型：
--
作者：
Nakahara, Yuko;Ozawa, Chinatsu;Nakahara, Yoshiaki
核心3和核心6 O-糖氨基酸是以保护形式制备的，适合于Fmoc固相肽合成(SPPS)。N-三氯乙酰乳糖胺衍生物(2)在受体314的3-O-糖基化和受体5/6的6-O-糖基化反应中被用作高度β-选择性糖基供体。锌还原三糖7/8和13/14后进行乙酰化，容易将三氯乙酰胺和叠氮基团转化为乙酰氨基。通过Pd(0)催化选择性脱保护，得到核心3 O-糖链构筑块11/12和核心6 O-糖链构筑块17/18。通过合成核心3-连接的MUC2串联重复序列糖肽和核心6-连接的糖肽片段，证明了这些构建块对SPPS的有效性。将合成的糖肽从树脂上分离出来，在“低酸度TfOH”条件下脱苄。(C)2007爱思唯尔有限公司。保留所有权利。
Core 3 and core 6 O-glycoamino acids were prepared in a protected form suited for Fmoc solid-phase peptide synthesis (SPPS). An N-trichloroacetyllactosamine derivative (2) was used as a highly beta-selective glycosyl donor in 3-O-glycosylation of acceptors 314 and in 6-O-glycosylation of acceptors 5/6. Zn reduction of trisaccharides 7/8 and 13/14 was followed by acetylation to readily transform trichloroacetamido and azido groups to acetamido groups. Selective deprotection by Pd(0)-catalysis afforded core 3 O-glycan building blocks 11/12 and core 6 O-glycan building blocks 17/18. Usefulness of these building blocks for SPPS was demonstrated by the syntheses of the core 3-linked MUC2 tandem repeat glycopeptide and the core 6-linked glycopeptide segment of MUC6. The synthetic glycopeptides detached from the resin were debenzylated under the 'low-acidity TfOH' conditions. (c) 2007 Elsevier Ltd. All rights reserved.