methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-α-D-glucopyranoside | 269065-36-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-α-D-glucopyranoside
• 英文别名: [(2R,3S,4R,5R,6S)-5-acetamido-4-benzoyloxy-3-hydroxy-6-methoxyoxan-2-yl]methyl benzoate
• CAS: 269065-36-3
• 化学式: C₂₃H₂₅NO₈
• 分子量: 443.453
• InChiKey: IZPGQJCFGTUCJN-ZFVCPDAYSA-N

物化性质

• 沸点：
  657.0±55.0 °C(Predicted)
• 密度：
  1.32±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  120
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-α-D-glucopyranoside 在 三氟甲磺酸三甲基硅酯 、 乙酰氯 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 methyl 2,3-di-O-benzoyl-α-D-mannopyranosyl-(1-> 4)-2-acetamido-3,6-di-O-benzoyl-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of two oligosaccharides, the GPI anchor glycans from S. cerevesiae and A. fumigatus

  摘要：

  Two oligosaccharides, alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 6)-alpha-D-Manp-(l --> 4)-alpha-D-GlcpNAc (I) and alpha-D-Manp-(1 --> 3)-alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 6)-alpha-D-Manp-(1 --> 4)-alpha-D-GlcpNAc (II), the glycosylphosphatidylinositol (GPI) anchor glycans from S. cerevesiae and A. fumigatus were synthesized as their methyl glycosides in a regio- and stereoselective manner. The pentasaccharide I was obtained from 6-O-selective glycosylation of methyl 2,3-di-O-benzoyl-alpha-D-mannopyranosyl-(l --> 4)-2-acetamido-3,6-di-O-benzoyl-2-deoxy-alpha-D-glucopyranoside (8) with 2-O-acetyl-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1 --> 2) -3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroacetimidate (9), followed by benzoylation, deacetylation, and mannosylation, and then by deprotection. The hexasaccharide (II) was obtained via condensation of allyl 3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(l --> 2)-3,4,6-tri-O-benzoyl-alpha-D-mannopyranoside (17) with 2,3,4,6-tetra-O-benzoyl-alpha-D-mannopyranosyl-(1 --> 3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl trichloroacetimidate (16), followed by deallylation, trichloroacetimidation, and coupling with acceptor (8), and finally by deprotection. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2003.09.030
• 作为产物：
  描述：

  D-GlcNAc 在 吡啶 、 对甲苯磺酸 、 溶剂黄146 、 乙酰氯 、 原甲酸三乙酯 作用下， 以 水 、 乙腈 为溶剂， 反应 13.0h， 生成 methyl 2-acetamido-3,6-di-O-benzoyl-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of two oligosaccharides, the GPI anchor glycans from S. cerevesiae and A. fumigatus

  摘要：

  Two oligosaccharides, alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 6)-alpha-D-Manp-(l --> 4)-alpha-D-GlcpNAc (I) and alpha-D-Manp-(1 --> 3)-alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 2)-alpha-D-Manp-(1 --> 6)-alpha-D-Manp-(1 --> 4)-alpha-D-GlcpNAc (II), the glycosylphosphatidylinositol (GPI) anchor glycans from S. cerevesiae and A. fumigatus were synthesized as their methyl glycosides in a regio- and stereoselective manner. The pentasaccharide I was obtained from 6-O-selective glycosylation of methyl 2,3-di-O-benzoyl-alpha-D-mannopyranosyl-(l --> 4)-2-acetamido-3,6-di-O-benzoyl-2-deoxy-alpha-D-glucopyranoside (8) with 2-O-acetyl-3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(1 --> 2) -3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl trichloroacetimidate (9), followed by benzoylation, deacetylation, and mannosylation, and then by deprotection. The hexasaccharide (II) was obtained via condensation of allyl 3,4,6-tri-O-benzoyl-alpha-D-mannopyranosyl-(l --> 2)-3,4,6-tri-O-benzoyl-alpha-D-mannopyranoside (17) with 2,3,4,6-tetra-O-benzoyl-alpha-D-mannopyranosyl-(1 --> 3)-2,4,6-tri-O-acetyl-alpha-D-mannopyranosyl trichloroacetimidate (16), followed by deallylation, trichloroacetimidation, and coupling with acceptor (8), and finally by deprotection. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2003.09.030

文献信息

• 3- and 4-Uloses Derived from N-Acetyl-D-glucosamine: A Unique Pair of Complementary Organocatalysts for Asymmetric Epoxidation of Alkenes
  作者：Christof Schöberl、Volker Jäger

  DOI：10.1002/adsc.201100735

  日期：2012.3.16

  The 4‐ulose and the 3‐ulose, both derived in two steps from the α‐methyl glycoside of N‐acetyl‐D‐glucosamine (GlcNAc), act as organocatalysts in the asymmetric epoxidation of alkenes, with unprecedented complementary enantioselectivity. The best results are found with α,β‐unsaturated esters as substrates, with enantiomeric ratios up to 90:10 and 11:89, respectively.

  N-乙酰基-D-葡糖胺（GlcNAc）的α-甲基糖苷（GlcNAc）分两步衍生出来的4-ulose和3-ulose在烯烃的不对称环氧化中起有机催化剂的作用，具有前所未有的互补对映选择性。以α，β-不饱和酯为底物发现最佳结果，对映体比例分别高达90:10和11:89。
• A comparative study of the influence of some protecting groups on the reactivity of d-glucosamine acceptors with a galactofuranosyl donor
  作者：María L. Bohn、María I. Colombo、Carlos A. Stortz、Edmundo A. Rúveda

  DOI：10.1016/j.carres.2006.03.030

  日期：2006.7

  experiments with a galactofuranosyl trichloroacetimidate donor were performed with glucosamine acceptors having a free 4-OH group and carrying different protecting groups at N-2, O-3, and O-6. The most reactive acceptor is the N-dimethylmaleimido 3,6-di-O-benzylated derivative (6c), which reacts even faster than the oxazolidinone 1a. Molecular orbital calculations have helped to rationalize these experimental

  使用具有游离4-OH基团且在N-2，O-3和O-6处带有不同保护基的葡糖胺受体，进行了半乳糖呋喃糖基三氯乙酰亚氨酸酯供体的竞争性糖基化实验。反应性最高的受体是N-二甲基马来酰亚胺基3,6-二-O-苄基化衍生物（6c），其反应甚至比恶唑烷酮1a还要快。分子轨道计算已根据供体和受体之间发生的硬-硬反应，帮助合理化了这些实验事实。
• Synthesis of a Glycosylphosphatidylinositol (GPI) Fragment as a Potential Substrate for Mannoprotein Transglycosidases
  作者：Tyson F. Belz

  DOI：10.1055/a-1523-1638

  日期：2021.12

  A glycophosphatidylinositol tetrasaccharide fragment was synthesized to mimic the core features of primary model, that of Saccharomyces cerevisiae. The salient feature of this approach is centered on the quick access to various α-1,2- and α-1,6-mannosyl and α-1,4-glycosyl linkages by using simple glycosylation and protective-group techniques. 1D and 2D-J-resolved NMR spectroscopy was used to verify the α-configuration of the new linkages. The tetrasaccharides obtained in this work are useful for examining fungal cell-wall glycoprotein cross-linking by transglycosidase enzymes for antifungal drug development.

  合成了一种含有四个糖基磷脂酰肌醇的碎片，以模拟酿酒酵母的原型核心特征。这种方法的显著特点在于使用简单的糖基化和保护基技术迅速获得各种α-1,2-和α-1,6-甘露糖基和α-1,4-糖基连接。使用1D和2D-J-解析NMR光谱验证了新连接的α-构型。本研究获得的四糖基物质对于研究真菌细胞壁糖蛋白交联和转糖酶酶类的抗真菌药物开发非常有用。

• Synthesis of 4-deoxy-4-fluoro analogues of 2-acetamido-2-deoxy-d-glucose and 2-acetamido-2-deoxy-d-galactose and their effects on cellular glycosaminoglycan biosynthesis
  作者：Ali Berkin、Walter A. Szarek*、Robert Kisilevsky*

  DOI：10.1016/s0008-6215(00)00049-5

  日期：2000.6

  4-Deoxy-4-fluoro analogues of 2-acetamido-2-deoxy-D-glucose and 2-acetamido-2-deoxy-D-galactose were synthesized and evaluated as inhibitors of hepatic glycosaminoglycan biosynthesis. 2-Acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-fluoro-D-glucopyranose (16) exhibited a reduction of [H-3]GlcN and [S-35]SO4 incorporation into hepatocyte cellular glycosaminoglycans to 12 and 18%, respectively, of the control cells, at 1.0 mM. Similarly, 2-acetamido-1,3,6-tri-O-acetyl-2,4-dideoxy-4-fluoro-D-gala (31) exhibited a reduction of [H-3]GlcN and [S-35]SO4 incorporation to 1 and 9%. respectively, of the control cells, at 1.0 mM. Unlike 16, 31 exhibited a reduction of [C-14]Leu incorporation into cellular protein to 57% of control cells, at 1.0 mM. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Inhibition of microbial β-N-acetylhexosaminidases by 4-deoxy- and galacto-analogues of NAG-thiazoline
  作者：Jana Krejzová、Lubica Kalachova、Petr Šimon、Helena Pelantová、Kristýna Slámová、Vladimír Křen

  DOI：10.1016/j.bmcl.2014.09.066

  日期：2014.11

  NAG-thiazoline is a well-established competitive inhibitor of two physiologically relevant glycosidase families-beta-N-acetylhexosaminidases (GH20) and beta-N-acetylglucosaminidases (GH84). Based on the different substrate flexibilities of these enzyme groups, we designed and synthesized the 4-deoxy derivative of NAG-thiazoline aiming at the selective inhibition of GH20 beta-N-acetylhexosaminidases. One GH84 and two GH20 microbial glycosidases were employed as model enzymes for the inhibition assays. Surprisingly, the new compound 4-deoxy-thiazoline exhibited no activity inhibition with either of the enzyme families of interest. Unlike with the substrates, the 4-hydroxyl group of the inhibitor's sugar ring seems to be crucial for binding the inhibitor to the active sites of these enzymes. (C) 2014 Elsevier Ltd. All rights reserved.