Efficient syntheses of core 1, core 2, core 3 and core 4 building blocks for SPS of mucin O-glycopeptides based on the N-Dts-method
Efficient syntheses of core 1, core 2, core 3 and core 4 building blocks for SPS of mucin O-glycopeptides based on the N-Dts-method
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DOI：
10.1039/p19960000985
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发表时间：
1996-05-21
期刊：
影响因子：
--
通讯作者：
Bock, K
中科院分区：
文献类型：
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作者：
Meinjohanns, E;Meldal, M;Bock, K
结构beta-D-Gal -(1——> 3)-alpha-D-GalNAc(1——> O) -L-Thr beta-D-Gal -(1——> 3)[beta-D-GlcNAc -(1——> 6)]-alpha-D-GalNAc——(1——> O) -L-Thr beta-D-GlcNAc -(1——> 3)-alpha-D-GalNAc(1——> O) -L-Thr和beta-D-GlcNAc -(1——> 3)[beta-D-GlcNAc -(1——> 6)]-alpha-D-GalNAc -(1——> O) -L-Thr代表1核心,核心2、3和4核心核心结构,分别的mucin-type O-glycoproteins,高效合成相应的构建块8,12、14和17。不同的n - α - fmoc - thr (α -d - galn (3))-OPfp衍生物与2-二硫代琥珀酰氨基糖基供体10进行立体选择性糖基化，然后在乙酸酐存在的情况下，用锌粉在四氢呋喃/乙酸中同时原位还原n -二硫代琥珀酰（N-Dts）和叠氮基，得到受保护的构建单元8、12、14和17。这些构建块可直接用于核1、核2、核3和核4粘蛋白o糖肽的固相合成（SPS），无需在固相上对碳水化合物部分进行进一步修饰。
The structures beta-D-Gal-(1-->3)-alpha-D-GalNAc-(1-->O)-L-Thr, beta-D-Gal-(1-->3)-[beta-D-GlcNAc-(1-->6)]-alpha-D-GalNAc-(1-->O)-L-Thr, beta-D-GlcNAc-(1-->3)-alpha-D-GalNAc-(1-->O)-L-Thr and beta-D-GlcNAc-(1-->3)-[beta-D-GlcNAc-(1-->6)]-alpha-D-GalNAc-(1-->O)-L-Thr represent the core 1, core 2, core 3 and core 4 structures, respectively, of mucin-type O-glycoproteins, Efficient syntheses of the corresponding building blocks 8, 12, 14 and 17 are described. Stereoselective glycosylation of different N-alpha-Fmoc-Thr(alpha-D-GalN(3))-OPfp derivatives with the 2-dithiasuccinimido glycosyl donor 10, followed by simultaneous in situ reduction of the N-dithiasuccinoyl (N-Dts) and azido functionalities with zinc dust in tetrahydrofuran/ acetic acid in the presence of acetic anhydride afforded the protected building blocks 8, 12, 14 and 17. These building blocks can be used directly in solid-phase synthesis (SPS) of core 1, core 2, core 3 and core 4 mucin O-glycopeptides, Further modification of the carbohydrate moiety on the solid phase is not required.