methyl 4,6-O-cyclohexylidene-2-O-p-methoxybenzyl-3-O-tert-butyldiphenylsilyl-1-thio-α-D-mannopyranoside | 215721-98-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4,6-O-cyclohexylidene-2-O-p-methoxybenzyl-3-O-tert-butyldiphenylsilyl-1-thio-α-D-mannopyranoside
• 英文别名: [(4aR,6R,7S,8S,8aR)-7-[(4-methoxyphenyl)methoxy]-6-methylsulfanylspiro[4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-2,1'-cyclohexane]-8-yl]oxy-tert-butyl-diphenylsilane
• CAS: 215721-98-5
• 化学式: C₃₇H₄₈O₆SSi
• 分子量: 648.936
• InChiKey: BJQIEWKJFCIGBP-HPRFQDQJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.69
• 重原子数：
  45
• 可旋转键数：
  10
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.51
• 拓扑面积：
  80.7
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-cyclohexylidene-2-O-p-methoxybenzyl-3-O-tert-butyldiphenylsilyl-1-thio-α-D-mannopyranoside 在 2,6-二叔丁基-4-甲基吡啶 、 4 A molecular sieve 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 三氟甲烷磺酸甲酯 作用下， 以 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 反应 14.0h， 生成 2-[(2S,3R,4R,5S,6R)-5-[(4aR,6S,7S,8R,8aR)-8-[tert-butyl(diphenyl)silyl]oxy-7-hydroxyspiro[4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-2,1'-cyclohexane]-6-yl]oxy-2-fluoro-4-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]isoindole-1,3-dione
  参考文献：
  名称：

  Synthesis of Monoglucosylated High-Mannose-Type Dodecasaccharide, a Putative Ligand for Molecular Chaperone, Calnexin, and Calreticurin

  摘要：

  Convergent and stereoselective synthetic routes to Man9GlcNAc2 (1b), alpha-Glc1M9GlcNAc2 (2b), and its stereoisomer beta-Glc1M9GlcNAc2 (3) were established. Interaction analysis of 2b with CRT was measured by 1H NMR spectroscopy, and the first NMR-based evidence for the specific binding of CRT to 2b was obtained.

  DOI：

  10.1021/ja021288q
• 作为产物：
  描述：

  甲基-2,3,4,6-四-O-乙酰基-1-硫代-Alpha-D-甘露糖苷 在 咪唑 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 sodium methylate 、 二异丁基氢化铝 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 39.5h， 生成 methyl 4,6-O-cyclohexylidene-2-O-p-methoxybenzyl-3-O-tert-butyldiphenylsilyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  Highly Optimized β-Mannosylation via p-Methoxybenzyl Assisted Intramolecular Aglycon Delivery

  摘要：

  使用甘露糖基硫代糖苷 5 和 19 实现了高效和立体选择性δ-甘露糖基化。在 MeOSO2CF3 的作用下，混合缩醛 12、15 和 20 中的苷元通过氧化偶联到 C-2 位带对甲氧基苄基（PMB）的甘露糖基硫代糖苷上，实现了分子内苷元传递（IAD），从而得到δ-甘露糖苷 13/16/21。值得注意的是，通过将 4-位和 6-位的保护基团从之前使用的亚苄基改为亚环己基（5）或 TIPDS（19）基团，IAD 的效率大大提高。因此，现在有可能以高度优化的方式进行δ-甘露糖基化，以 75%-85% 的产率获得具有与天冬酰胺连接的低聚糖相对应的骨架结构的二糖和三糖单个立体异构体。

  DOI：

  10.1055/s-1998-1894

文献信息

• On the mechanism of p-methoxybenzylidene assisted intramolecular aglycon delivery
  作者：Yukishige Ito、Hiromune Ando、Megumi Wada、Tsubasa Kawai、Yuki Ohnish、Yoshiaki Nakahara

  DOI：10.1016/s0040-4020(01)00300-3

  日期：2001.5

  p-Methoxybenzylidene-assisted intramolecular aglycon delivery was developed in this laboratory and has been demonstrated to be highly efficient and versatile particularly for the synthesis of complex glycoprotein-related glycans. It was revealed that the reaction course of IAD can be clearly monitored by performing the reaction in an NMR tube. Our results suggest that the nonhydrolytic pathway that

  在该实验室中开发了对甲氧基苄叉基辅助的分子内糖苷配基递送，并且已被证明是高效且通用的，特别是对于复杂糖蛋白相关聚糖的合成。揭示了通过在NMR管中进行反应可以清楚地监测IAD的反应过程。我们的结果表明，将亚稳态中间体3转化为产物的非水解途径是有功能的。在反应介质中存在和不存在水的情况下进行的对比实验提供了支持性证据，消除了在标准IAD条件下水被偶然污染的可能性。
• Comprehensive synthesis of ER related high-mannose-type sugar chains by convergent strategy
  作者：Ichiro Matsuo、Kiichiro Totani、Atsushi Tatami、Yukishige Ito

  DOI：10.1016/j.tet.2006.06.045

  日期：2006.8

  Systematic synthesis of high-mannose-type sugar chains of asparagine-linked glycoproteins is described. To construct the target sugar chains, we employed the convergent route, using three oligosaccharide components, the common hexasaccharide, branched tri-, tetra- and pentasaccharides, and mono-, di-, and triglucosyl fragments. Construction of the β-mannoside linkage was performed using p-methoxybenzyl-assisted

  描述了天冬酰胺连接的糖蛋白的高甘露糖型糖链的系统合成。为了构建目标糖链，我们采用了收敛途径，使用了三种低聚糖成分：普通六糖，支链三糖，四糖和五糖以及单糖，二糖和三糖基片段。使用p进行β-甘露糖苷键的构建-甲氧基苄基辅助的分子内糖苷配基递送。将六糖片段与支链甘露寡糖供体（例如M5，M4B，M4C和M3）偶联，分别得到十一碳糖（M9），十糖（M8B和M8C）和九糖（M7）。结合它们的单，二和三葡萄糖基片段分别得到十四碳糖（G3M9），十三碳糖（G2M9），十二碳糖（G1M9），十一碳糖（G1M8B和G1M8C）和十碳糖（G1M7）。
• Amino acid fluoride for glycopeptide synthesis
  作者：Yukishige Ito、Manfred Gerz、Yoshiaki Nakahara

  DOI：10.1016/s0040-4039(99)02228-5

  日期：2000.2

  The formation of N-glycosidic linkage between N-acetylglucosamine (GlcNAc) and asparagine (Asn) was effected using aspartic acid gamma-fluoride in combination with either glycosyl azide or silyl carbamate, by the action of Lindlar catalyst or Bu4NF Further elongation of peptide chain was performed to give pentapeptide. This method was further applied into the synthesis of trisaccharidic asparagine, using beta-methoxybenzyl assisted stereoselective B-mannosylation as the key transformation. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis of anα-(2,3)-Sialylated, Complex-Type Undecasaccharide
  作者：Joachim Seifert、Matthias Lergenmüller、Yukishige Ito

  DOI：10.1002/(sici)1521-3773(20000204)39:3<531::aid-anie531>3.0.co;2-f

  日期：2000.2.4
• Desilylation under high pressure
  作者：Ichiro Matsuo、Megumi Wada、Yukishige Ito

  DOI：10.1016/s0040-4039(02)00538-5

  日期：2002.4

  Cleavage of tert-butyldiphenylsilyl (TBDPS) ether was examined under high pressure conditions (1.0 GPa) using HF pyridine in DMF. This method proved to be exceptionally suitable for deprotecting the TBDPS group that resides at the sterically hindered position. Under these conditions, various types of other hydroxyl protecting groups (i.e. benzyl, p-methoxybenzyl, trityl, isopropylidene, cyclohexylidene, allyl, phthaloyl) as well as O- and S-glycosidic linkages were preserved. (C) 2002 Elsevier Science Ltd. All rights reserved.