2-methyl-4,5-dihydro-[4-O-(β-D-glucopyranosyl)-1,2-dideoxy-α-D-glucopyranoso][2,1-d]-1,3-oxazole | 191532-19-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-methyl-4,5-dihydro-[4-O-(β-D-glucopyranosyl)-1,2-dideoxy-α-D-glucopyranoso][2,1-d]-1,3-oxazole
• 英文别名: (2S,3R,4S,5S,6R)-2-[[(3aR,5R,6S,7R,7aR)-7-hydroxy-5-(hydroxymethyl)-2-methyl-5,6,7,7a-tetrahydro-3aH-pyrano[3,2-d][1,3]oxazol-6-yl]oxy]-6-(hydroxymethyl)oxane-3,4,5-triol
• CAS: 191532-19-1
• 化学式: C₁₄H₂₃NO₁₀
• 分子量: 365.337
• InChiKey: HHZZJXOUIQVBPC-JVWNEXKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -3.8
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  171
• 氢给体数：
  6
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  2-methyl-4,5-dihydro-[4-O-(β-D-glucopyranosyl)-1,2-dideoxy-α-D-glucopyranoso][2,1-d]-1,3-oxazole 、 Nα-(benzyloxycarbonyl)-Nγ-(2-acetamido-2-deoxy-β-D-glucopyranosyl)-L-asparagine O-methyl ester 在 endohexosaminidase A 作用下， 以48%的产率得到N4-[β-D-glucopyranosyl-(1->4)-2-acetamido-2-deoxy-β-D-glucopyranosyl-(1->4)-2-acetamido-2-deoxy-β-D-glucopyranosyl]-N2-(benzyloxycarbonyl)-L-asparagine methyl ester
  参考文献：
  名称：

  内己糖胺酶催化的恶唑啉供体糖基化：催化效率和可逆性的微调。

  摘要：

  合成了一系列完整的恶唑啉二糖、三糖、四糖和六糖，对应于 N-连接糖蛋白高甘露糖聚糖的核心部分，以及相应的含有中心葡萄糖单元的寡糖，并作为糖基供体进行了测试。由内己糖胺酶 M (Endo M)、A (Endo A) 和 H (Endo H) 催化的 GlcNAcAsn 糖基氨基酸的糖基化。虽然 Endo H 没有催化任何糖基化反应，但 Endo M 和 Endo A 都有效地催化了糖基化，这些糖基化不仅限于包含 Manbeta(1-->4)GlcNAc 链接的供体。精确的结构活性关系和时间进程研究揭示了与所用酶和精确恶唑啉结构相关的合成过程效率的微调。Endo M 和 Endo A 均可实现有效的不可逆糖基化，进一步证明使用结构修饰的恶唑啉供体作为过渡态模拟物以促进酶催化合成，同时防止产物水解；在这些情况下，酶表现出“糖基连接酶”活性。

  DOI：

  10.1002/chem.200800365
• 作为产物：
  描述：

  2',3',4',6'-tetra-O-acetyl-β-D-glucopyranosyl-(1→4)-3,6-di-O-acetyl-2-azido-2-deoxy-1-O-nitro-β-D-glucopyranose 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 、 sodium acetate 、 溶剂黄146 作用下， 以 甲醇 、 1,2-二氯乙烷 为溶剂， 反应 4.0h， 生成 2-methyl-4,5-dihydro-[4-O-(β-D-glucopyranosyl)-1,2-dideoxy-α-D-glucopyranoso][2,1-d]-1,3-oxazole
  参考文献：
  名称：

  GLYCOPROTEIN SYNTHESIS AND REMODELING BY ENZYMATIC TRANSGLYCOSYLATION

  摘要：

  公开号：

  EP2001358B1

文献信息

• Glycopeptide Synthesis throughendo-Glycosidase-Catalyzed Oligosaccharide Transfer of Sugar Oxazolines: Probing Substrate Structural Requirement
  作者：Ying Zeng、Jingsong Wang、Bing Li、Steven Hauser、Hengguang Li、Lai-Xi Wang

  DOI：10.1002/chem.200501196

  日期：2006.4.12

  An array of sugar oxazolines was synthesized and tested as donor substrates for the Arthrobacter endo-beta-N-acetylglucosaminidase (Endo-A)-catalyzed glycopeptide synthesis. The experiments revealed that the minimum structure of the donor substrate required for Endo-A catalyzed transglycosylation is a Man beta1-->4-GlcNAc oxazoline moiety. Replacement of the beta-D-Man moiety with beta-D-Glc, beta-D-Gal

  合成了一系列糖恶唑啉，并测试了它们作为节杆菌内-β-N-乙酰氨基葡糖苷酶（Endo-A）催化的糖肽合成的供体底物。实验表明，Endo-A催化转糖基化所需的供体底物的最小结构是Man beta1-> 4-GlcNAc恶唑啉部分。用β-D-Glc，β-D-Gal和β-D-GlcNAc单糖替代β-D-Man部分会导致二糖恶唑啉的底物活性降低。尽管如此，该酶仍可耐受修饰，例如在β-D-Man部分的3和/或6位上附加糖残基或官能团的连接，从而使选择性修饰的寡糖成功转移到肽上受体。另一方面，该酶在受体部分具有很大的柔韧性，可以同时使用大大小小的GlcNAc肽作为受体。研究表明，内切糖苷酶催化的转糖基化在构建天然和选择性修饰糖肽方面都具有巨大潜力。
• Endo-β-N-acetylglucosaminidase-catalyzed polymerization of β-Glcp-(1→4)-GlcpNAc oxazoline: a revisit to enzymatic transglycosylation
  作者：Hirofumi Ochiai、Wei Huang、Lai-Xi Wang

  DOI：10.1016/j.carres.2009.01.016

  日期：2009.3

  An alternative synthesis of beta-Glcp-(1 -> 4)-GlcpNAc oxazoline is described, and its enzymatic reaction with the endo-beta-N-acetylglucosaminidase from Arthrobacter protophormiae (Endo-A) was re-investigated. Under normal transglycosylation conditions with a catalytic amount of enzyme, Enclo-A showed only marginal activity for transglycosylation with the disaccharide oxazoline, consistent with our previous observations. However, when used in a relatively large quantity, Endo-A could promote the transglycosylation of the disaccharide oxazoline to a GlcpNAc-Asn acceptor. In addition to the initial transglycosylation product, a series of large oligosaccharides were also formed due to the tandem transglycosylation to the terminal glucose residues in the intermediate products. In the absence of an external acceptor, Enclo-A could polymerize the disaccharide oxazoline to form oligo- and polysaccharides having the -4-beta-(Glcp-(1 -> 4)-beta-GlcpNAc)-1-repeating units. This is the first example of an endo-beta-N-acetylglucosaminidase-promoted polymerization of activated oligosaccharide substrates. This enzymatic polymerization may find useful applications for the synthesis of novel artificial polysaccharides. (C) 2009 Elsevier Ltd. All rights reserved.
• GLYCOPROTEIN SYNTHESIS AND REMODELING BY ENZYMATIC TRANSGLYCOSYLATION
  申请人：University Of Maryland, Baltimore

  公开号：EP2001358B1

  公开（公告）日：2016-07-13
• Endohexosaminidase-Catalysed Glycosylation with Oxazoline Donors: Fine Tuning of Catalytic Efficiency and Reversibility
  作者：Thomas W. D. F. Rising、Christoph D. Heidecke、James W. B. Moir、Zhenlian Ling、Antony J. Fairbanks

  DOI：10.1002/chem.200800365

  日期：2008.7.18

  A complete series of oxazoline di-, tri-, tetra-, and hexasaccharides, corresponding to the core sections of N-linked glycoprotein high mannose glycans, together with the corresponding oligosaccharides containing a central glucose unit, were synthesised and tested as glycosyl donors for glycosylation of a GlcNAcAsn glycosyl amino acid catalysed by the endohexosaminidases M (Endo M), A (Endo A) and

  合成了一系列完整的恶唑啉二糖、三糖、四糖和六糖，对应于 N-连接糖蛋白高甘露糖聚糖的核心部分，以及相应的含有中心葡萄糖单元的寡糖，并作为糖基供体进行了测试。由内己糖胺酶 M (Endo M)、A (Endo A) 和 H (Endo H) 催化的 GlcNAcAsn 糖基氨基酸的糖基化。虽然 Endo H 没有催化任何糖基化反应，但 Endo M 和 Endo A 都有效地催化了糖基化，这些糖基化不仅限于包含 Manbeta(1-->4)GlcNAc 链接的供体。精确的结构活性关系和时间进程研究揭示了与所用酶和精确恶唑啉结构相关的合成过程效率的微调。Endo M 和 Endo A 均可实现有效的不可逆糖基化，进一步证明使用结构修饰的恶唑啉供体作为过渡态模拟物以促进酶催化合成，同时防止产物水解；在这些情况下，酶表现出“糖基连接酶”活性。