3,6-di-O-benzyl-1-O-tert-butyldimethylsilyl-2-deoxy-2-phthalimido-β-D-glucopyranose | 514792-62-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,6-di-O-benzyl-1-O-tert-butyldimethylsilyl-2-deoxy-2-phthalimido-β-D-glucopyranose
• 英文别名: tert-butyldimethylsilyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-β-D-glucopyranoside；t-butyldimethylsilyl 2-deoxy-3,6-di-O-benzyl-2-phthalimido-beta-d-glucopyranoside；2-[(2S,3R,4R,5S,6R)-2-[tert-butyl(dimethyl)silyl]oxy-5-hydroxy-4-phenylmethoxy-6-(phenylmethoxymethyl)oxan-3-yl]isoindole-1,3-dione
• CAS: 514792-62-2
• 化学式: C₃₄H₄₁NO₇Si
• 分子量: 603.788
• InChiKey: RVXAWVODTNSZLC-ZKFZROEQSA-N

物化性质

• 沸点：
  678.6±55.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  43
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  94.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,6-di-O-benzyl-1-O-tert-butyldimethylsilyl-2-deoxy-2-phthalimido-β-D-glucopyranose 在 四丁基氟化铵 、 sodium hydride 、 肼 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 甲醇 、 正庚烷 、 乙基苯 、 N,N-二甲基甲酰胺 为溶剂， 反应 97.25h， 生成 2-acetamido-3,6-di-O-benzyl-2-deoxy-4-O-methyl-α-D-glucopyranose 1-dibenzylphosphate
  参考文献：
  名称：

  Chemical synthesis of UDP-4-O-methyl-GlcNAc, a potential chain terminator of chitin synthesis

  摘要：

  Chitin synthase converts uridine diphosphoryl-N-acetylglucosamine (UDP-GlcNAc) to chitin (poly-beta-(1 --> 4)-GlcNAc). During polymerization, elongation occurs at the 4-OH (nonreducing) terminus of the growing chitin chain. Blockage of the 4-OH via incorporation of UDP-N-acetyl-4-O-methylglucosamine (UDP-4-OMe-GlcNAc, 3) can potentially terminate chitin polymerization, and represents a novel strategy for chitin synthase inhibition. The chemical synthesis of 3 and preliminary evaluation of its possible incorporation by chitin synthase are reported herein. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2004.03.014
• 作为产物：
  描述：

  tert-butyldimethylsilyl 4,6-O-benzylidene-2-deoxy-2-phthalimido-β-D-glucopyranoside 在 三乙基硅烷 、 四丁基碘化铵 、 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 0.5h， 生成 3,6-di-O-benzyl-1-O-tert-butyldimethylsilyl-2-deoxy-2-phthalimido-β-D-glucopyranose
  参考文献：
  名称：

  Selection of protecting groups and synthesis of a β-1,4-GlcNAc-β-1,4-GlcN unit

  摘要：

  The synthesis of the disaccharide tert-butyldimethylsilyl (4-O-acetyl-2-azido-3,6-di-O-benzyl-2-deoxy-beta-D-glucopyranosyl)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-beta-D-glucopyranoside, designed as a repeating unit appearing in oligo-and polysaccharides, which exhibits a distinguished "obverse-reverse" property in beta-1,4-glucan chain, was accomplished. This disaccharide was synthesized by glycosylation of a phthalimido sugar with an azido sugar. A selective removal of the two different protecting groups atC-2 for obtaining 2-acetamido-4-O-(2-amino-2-deoxy-beta-D-glucopyranosyl)-2-deoxy-beta-D-glucopyranose indicates that the selection and combination, using phthalimido and azido as protecting groups, are an excellent strategy for synthesizing such target disaccharides.

  DOI：

  10.1007/s00706-009-0172-0

文献信息

• Stereoselective Direct Glycosylation with Anomeric Hydroxy Sugars by Activation with Phthalic Anhydride and Trifluoromethanesulfonic Anhydride Involving Glycosyl Phthalate Intermediates
  作者：Kwan Soo Kim、Dinanath Baburao Fulse、Ju Yuel Baek、Bo-Young Lee、Heung Bae Jeon

  DOI：10.1021/ja710935z

  日期：2008.7.1

  by sequential addition of DTBMP and Tf2O and glycosyl acceptors to the reaction mixture at -78 degrees C in one-pot. Stereoselective alpha-glucopyranosylations with 2,3-di-O-benzyl-4,6-O-benzylidene-D-glucopyranose (25) and other glycosylations with glucopyranoses and mannopyranoses having tetra-O-benzyl- and tetra-O-benzoyl protecting groups were also possible by utilizing the present one-pot glycosylation

  已经开发了一种以异头羟基糖为糖基供体、使用邻苯二甲酸酐和三氟甲磺酸酐作为活化剂的有效直接一锅糖基化方法。因此，通过 2,3-di-O-benzyl-4,6-O-benzylidene-D-mannopyranose (2) 与邻苯二甲酸酐在 DBU 存在下在室温下反应，实现了高度立体选择性的 β-吡喃甘露糖基化在-78 摄氏度的一锅中将 DTBMP 和 Tf2O 以及糖基受体依次添加到反应混合物中。具有 2,3-二-O-苄基-4,6-O-亚苄基-D-吡喃葡萄糖 (25) 的立体选择性 α-吡喃葡萄糖基化和具有四-O-苄基-和四-O-苯甲酰基保护的吡喃葡萄糖和吡喃甘露糖的其他糖基化通过使用目前的一锅糖基化方案，也可以进行分组。基于 NMR 研究提出了与 2 β-甘露糖基化的可能机制，其中检测到 α-甘露糖基邻苯二甲酸酯 55alpha 和 α-甘露糖基三氟甲磺酸酯 59 作为中间体。本糖基化方法的多功能性和效率，尤其是
• Manual and Automated Syntheses of the N-Linked Glycoprotein Core Glycans
  作者：Salvatore G. Pistorio、Scott A. Geringer、Keith J. Stine、Alexei V. Demchenko

  DOI：10.1021/acs.joc.8b03056

  日期：2019.6.7

  Presented herein are two complementary approaches to the synthesis of the core N-glycan pentasaccharide. The first, a traditional manual approach in solution, makes use of the H-bond-mediated aglycone delivery method for the highly diastereoselective introduction of the β-mannosidic linkage at room temperature. The synthesis of the core pentasaccharide was also accomplished using an high-performance

  本文提出了两种合成核心N-聚糖五糖的互补方法。第一种方法是传统的手动解决方法，它利用H键介导的糖苷配基传递方法在室温下非对映选择性地引入β-甘露糖苷键。核心五糖的合成也使用高效液相色谱辅助的自动化方法完成。总体组装迅速（8小时），效率高（31％）。
• Construction of<i>N</i>-Glycan Microarrays by Using Modular Synthesis and On-Chip Nanoscale Enzymatic Glycosylation
  作者：Sonia Serna、Juan Etxebarria、Nerea Ruiz、Manuel Martin-Lomas、Niels-Christian Reichardt

  DOI：10.1002/chem.201001295

  日期：2010.11.22

  An effective chemoenzymatic strategy is reported that has allowed the construction, for the first time, of a focused microarray of synthetic N‐glycans. Based on modular approaches, a variety of N‐glycan core structures have been chemically synthesized and covalently immobilized on a glass surface. The printed structures were then enzymatically diversified by the action of three different glycosyltransferases

  据报道，一种有效的化学酶策略首次允许构建合成的N-聚糖聚焦微阵列。基于模块化方法，各种N‐聚糖核心结构已化学合成并共价固定在玻璃表面上。然后，通过印刷机器人，通过置于微阵列各个点顶部的纳米液滴中的三种不同糖基转移酶的作用，使印刷的结构酶促多样化。转化之后是对末端糖具有特异性的凝集素结合。与溶液相中进行的反应相比，纳米液滴中表面结合配体的这种酶促延伸将所需的珍贵糖基转移酶的数量减少了七个数量级。此外，仅可以选择已显示为特定糖基转移酶底物的那些配体以在阵列上延伸。这里描述的方法，
• Synthesis of a core trisaccharide building block for the assembly of N-glycan neoconjugates
  作者：Sonia Serna、Bharat Kardak、Niels-Christian Reichardt、Manuel Martin-Lomas

  DOI：10.1016/j.tetasy.2009.02.028

  日期：2009.5

  A short and high yielding synthesis of a core trisaccharide 1 as the key building block in the assembly of a library of N-glycan neoconjugates is presented. The beta-D-Manp-(1 -> 4)-D-GlcpNAc linkage was introduced by inversion of the C-2 position of a beta-glucoside. The glucosyl donor was efficiently synthesised following a recently published one-pot strategy. 2-Naphthylmethyl and benzylidene-acetal protection in the terminal mannose permitted selective liberation of main branching sites for subsequent glycosylation. A C5 azido linker attached to the anomeric position, which is stable throughout the synthesis, will allow for the posterior immobilisation of deprotected glycans on a microarray surface. (C) 2009 Elsevier Ltd. All rights reserved.
• Chemical synthesis of UDP-4-O-methyl-GlcNAc, a potential chain terminator of chitin synthesis
  作者：Robert Chang、Philip Moquist、Nathaniel S Finney

  DOI：10.1016/j.carres.2004.03.014

  日期：2004.6

  Chitin synthase converts uridine diphosphoryl-N-acetylglucosamine (UDP-GlcNAc) to chitin (poly-beta-(1 --> 4)-GlcNAc). During polymerization, elongation occurs at the 4-OH (nonreducing) terminus of the growing chitin chain. Blockage of the 4-OH via incorporation of UDP-N-acetyl-4-O-methylglucosamine (UDP-4-OMe-GlcNAc, 3) can potentially terminate chitin polymerization, and represents a novel strategy for chitin synthase inhibition. The chemical synthesis of 3 and preliminary evaluation of its possible incorporation by chitin synthase are reported herein. (C) 2004 Elsevier Ltd. All rights reserved.