methyl 2-acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside | 144789-65-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 2-acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside
• 英文别名: methyl 2-acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-allopyranoside
• CAS: 144789-65-1
• 化学式: C₂₃H₂₇NO₆
• 分子量: 413.47
• InChiKey: CAHYTBCORGHKHX-RCQJKQRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.56
• 重原子数：
  30.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  75.25
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 盐酸 、 sodium cyanoborohydride 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 13.0h， 生成 methyl N,N-diacetyl-2-amino-2-deoxy-3,6-di-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  Why Are the Hydroxy Groups of Partially Protected N-Acetylglucosamine Derivatives Such Poor Glycosyl Acceptors, and What Can Be Done about It? A Comparative Study of the Reactivity of N-Acetyl-, N-Phthalimido-, and 2-Azido-2-deoxy-glucosamine Derivatives in Glycosylation. 2-Picolinyl Ethers as Reactivity-Enhancing Replacements for Benzyl Ethers

  摘要：

  Competition experiments were used to determine that the 4-OH of a 2-deoxy-2-azidoglucose derivative is more reactive than that of the corresponding N-phthalimido glucose derivative which, in turn, is more easily glycosylated than the N-acetyl derivative. Glycosylation of the C-OH groups of the N,N-diacetyl and N-acetyl-N-benzyl glucosamine was also found to be superior to that of the simple N-acetyl substance. The 3-O-picolinyl ether of a 4,6-O-benzylidene-protected N-acetylglucosamine was shown to have a strong intramolecular hydrogen bond to the adjacent acetamide group. This interaction does not persist in the 3-O-picolinyl-6-O-benzyl N-acetylglucosamine derivative. owing to a probable competing hydrogen bond between the 4-OH and the picolinyl ether. However, in the 3-O-picolinyl-4-O-benzyl N-acetylglucosamine regioisomer the picolinyl-acetamide hydrogen bond persists and leads to an enhancement of reactivity of the 6-OH, over and above that in the corresponding 3-O-benzyl ether. due to disruption of the typical intermolecular amide hydrogen bonding scheme. It is demonstrated that the picolinyl ether is readily removed by hydrogenolysis at atmospheric pressure and room temperature.

  DOI：

  10.1021/ja010086b
• 作为产物：
  描述：

  溴甲苯 、 methyl 2-acetamido-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 methyl 2-acetamido-3-O-benzyl-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  A 1-acetamido derivative of 6-epi-valienamine: an inhibitor of a diverse group of β-N-acetylglucosaminidases

  摘要：

  本文介绍了一种带有乙酰氨基的 6-epi-valienamine 类似物的合成及其作为 β-N- 乙酰葡糖胺酶抑制剂的特性。该化合物对人类 O-GlcNA 酶和人类 δ-hexosaminidase 以及两种细菌 δ-N-acetylglucosaminidases 都有很好的抑制作用。Bacteroides thetaiotaomicron BtGH84 与该抑制剂复合物的三维结构显示，不饱和环发生了令人惊讶的扭曲，偏离了其最喜欢的溶液相构象，揭示了提高抑制剂效力的潜力。

  DOI：

  10.1039/b709681j

文献信息

• Glycosylidene Carbenes. Part 13. Synthesis and thermolysis of representative 1-azi-glycoses
  作者：Andrea Vasella、Christian Witzig、Christian Waldraff、Peter Uhlmann、Karin Briner、Bruno Bernet、Luigi Panza、Ren� Husi

  DOI：10.1002/hlca.19930760811

  日期：1993.12.15

  compatible with the hypothesis of a heterolytic cleavage of a CN bond. An early transition state is evidenced by the absence of torsional strain by an annulated 1,3-dioxane ring. Thermolysis of 1 in MeCN at 23° led mostly to the diasteroisomeric (Z,Z)-, (E,E)-, and (E,Z)-lactone azines 56, 57, and 58 (Scheme 6), which convert to 56 under mild conditions, and to 59 (3%). The benzyloxyglucal 59 was obtained

  在假设alkoxydiazirines的热解（在postlating CN键的异裂的上下文中方案1）中，我们报告了diazirines的制备4，5，7，和8，对于在diazirines的MeOH中热解的动力学参数1和4–9以及它们在非质子环境中的热解产物。的diazirines 4，57，和8（方案2-5）从已知的半缩醛制备10，19，34（从制备31（以改进的方式），并根据已建立的方法42。肟11，20，35，和43分别从相应的半缩醛作为（得到E / Z）-mixtures; 43是与环状羟胺一起形成44。氧化11，35，和43（Ñ氯琥珀酰亚胺/ 1,8-二氮杂双环[5.4.0]十一碳-7-烯（NCS / DBU）或的NaIO 4），得到（的良好的产率Ž）-hydroximolactones 12，36和45，而肟20导致产生（E）-和（Z）-氢氧内酯21和22的混合物，其采用不同的构象
• Synthesis and Glycosylation Properties of C6-Silylated <i>Ido</i> - and <i>Gluco</i> -Pyranosyl Donors
  作者：Ignacio Álvarez-Martínez、Christian Marcus Pedersen

  DOI：10.1002/ejoc.202000708

  日期：2020.8.9

  To study the influence of a silyl group on the reactivity and selectivity of glycosyl donors, two synthetic routes have been developed to obtain both d ‐glucosyl and l ‐idosyl donors with a silyl group attach to C6. The glycosylation and competition studies show that it enhances reactivity beyond what an O‐benzyl group on C6 would do. In order to access C6‐deoxy sugars, an efficient protodesilylation

  为了研究反应性和糖捐助者的选择性甲硅烷基的影响，两种合成路线已发展到同时获得d -glucosyl和升-idosyl与甲硅烷基捐助者附加到C6。糖基化和竞争研究表明，它增强了反应性，超过了C6上的O-苄基。为了获得C6-脱氧糖，还描述了一种有效的原去甲硅烷基化方法。
• DISAL glycosyl donors for efficient glycosylations under acidic conditions: Application to solid-phase oligosaccharide synthesis
  作者：Lars Petersen、Knud J. Jensen

  DOI：10.1039/b105872j

  日期：——

  The use of DISAL (methyl dinitrosalicylate) glycosyl donors in efficient Lewis acid-promoted glycosylations is reported. N-Acetyl-D-glucosamine monosaccharide acceptors are successfully glycosylated at O-6 or O-4 using benzyl- and benzoyl-protected DISAL donors in CH2Cl2 or nitromethane in the presence of LiClO4. The resultant disaccharides are isolated in yields ranging from 35 to 93%. Other Lewis acids such as FeCl3, TMSOTf, or BF3·Et2O also prove efficient for glycosylation of the secondary alcohol cyclohexanol. However, for the synthesis of disaccharides, the mild activation by LiClO4 gives higher yields. This approach is extended to efficient solid-phase glycosylation of a D-glucosamine derivative anchored by the 2-amino group through a Backbone Amide Linker (BAL) to a polystyrene support.

  报告了在高效的路易斯酸促进糖基化反应中使用 DISAL（二硝基水杨酸甲酯）糖基供体的情况。在 CH2Cl2 或硝基甲烷中，在 LiClO4 的存在下，使用苄基和苯甲酰基保护的 DISAL 给体成功地在 O-6 或 O-4 处糖基化了 N-乙酰基-D-氨基葡萄糖单糖受体。由此分离出的二糖收率在 35% 到 93% 之间。其他路易斯酸（如 FeCl3、TMSOTf 或 BF3-Et2O）也被证明能有效地对仲醇环己醇进行糖基化。不过，在合成二糖时，LiClO4 的温和活化可获得更高的产量。这种方法扩展到了通过骨架酰胺连接物（BAL）将 2-氨基锚定在聚苯乙烯支架上的 D-氨基葡萄糖衍生物的高效固相糖基化。