methyl 2-acetamido-6-O-benzyl-2-N,3-O-carbonyl-2-deoxy-α-D-glucopyranoside | 526199-44-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-6-O-benzyl-2-N,3-O-carbonyl-2-deoxy-α-D-glucopyranoside
• 英文别名: (3aR,4S,6R,7S,7aR)-3-acetyl-7-hydroxy-4-methoxy-6-(phenylmethoxymethyl)-4,6,7,7a-tetrahydro-3aH-pyrano[3,4-d][1,3]oxazol-2-one
• CAS: 526199-44-0
• 化学式: C₁₇H₂₁NO₇
• 分子量: 351.356
• InChiKey: ZSAKUEWNPLLEBD-QCODTGAPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  25
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  methyl 2-acetamido-6-O-benzyl-2-N,3-O-carbonyl-2-deoxy-α-D-glucopyranoside 在 barium dihydroxide 、 1-(苯基亚硫酰基)哌啶 、 三氟甲磺酸酐 、 2,4,6-三叔丁基嘧啶 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 11.17h， 生成 methyl 2-acetamido-6-O-benzyl-2-deoxy-[2,3-di-O-benzyl-4,6-O-benzylidene-α-D-glucopyranosyl]-(1->4)-α-D-glucopyranoside
  参考文献：
  名称：

  Oxazolidinone Protection of N-Acetylglucosamine Confers High Reactivity on the 4-Hydroxy Group in Glycosylation

  摘要：

  [GRAPHICS]The preparation of a convenient oxazolidinone protected N-acetyl glucosamine 4-OH derivative is reported. This substance exhibits enhanced reactivity as a glycosyl acceptor in a variety of coupling methods, the products of which are converted to the target N-acetylglucosaminyl saccharides under very mild conditions.

  DOI：

  10.1021/ol0342305
• 作为产物：
  描述：

  methyl 2-amino-4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 在 盐酸 、 sodium cyanoborohydride 、 碳酸氢钠 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 10.5h， 生成 methyl 2-acetamido-6-O-benzyl-2-N,3-O-carbonyl-2-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  6- O-苄基-和6 - O-甲硅烷基-N-乙酰基-2-氨基-2- N，3 - O-羰基-2-脱氧葡糖苷：氨基葡萄糖4-OH系列中的有效糖基受体。端基立体化学对去除恶唑烷酮基的影响

  摘要：

  N-乙酰氨基葡糖的α-和β-甲基糖苷的4-OH基团，在氮和O-3上被恶唑烷酮保护，在O-6上具有苄基或甲硅烷基保护基，在与N偶联时作为受体具有出色的反应性一系列糖基供体。这些受体增强的反应性部分归因于恶唑烷酮的束缚性质，其减少了亲核氧周围的阻碍。的Ñ -acetyloxazolidinone功能也降低了在简单看到的倾向Ñ朝向酰胺糖基化-acetylglucosamines，并去除有问题的氢键网络的可能性。在β-而不是α-序列中，N-乙酰基恶唑烷酮直接选择性水解为N-乙酰氨基葡糖可能与氢氧化钡结合使用，该特征归因于乙酰胺羰基与β系列糖苷氧之间形成螯合物。

  DOI：

  10.1021/jo0482559

文献信息

• 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。
• Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a <i>trans</i>-Fused 2,3-<i>O</i>-Carbonate Group
  作者：David Crich、Prasanna Jayalath

  DOI：10.1021/jo0508999

  日期：2005.9.1

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.
• 6-<i>O</i>-Benzyl- and 6-<i>O</i>-Silyl-<i>N</i>-acetyl-2-amino-2-<i>N</i>,3-<i>O</i>-carbonyl-2-deoxyglucosides:  Effective Glycosyl Acceptors in the Glucosamine 4-OH Series. Effect of Anomeric Stereochemistry on the Removal of the Oxazolidinone Group
  作者：David Crich、A. U. Vinod

  DOI：10.1021/jo0482559

  日期：2005.2.1

  protected with an oxazolidinone spanning the nitrogen and O-3, and bearing benzyl or silyl protection on O-6, show excellent reactivity as acceptors in couplings to a range of glycosyl donors. The enhanced reactivity of these acceptors is attributed in part to the tied back nature of the oxazolidinone, which reduces hindrance around the nucleophilic oxygen. The N-acetyloxazolidinone function also reduces

  N-乙酰氨基葡糖的α-和β-甲基糖苷的4-OH基团，在氮和O-3上被恶唑烷酮保护，在O-6上具有苄基或甲硅烷基保护基，在与N偶联时作为受体具有出色的反应性一系列糖基供体。这些受体增强的反应性部分归因于恶唑烷酮的束缚性质，其减少了亲核氧周围的阻碍。的Ñ -acetyloxazolidinone功能也降低了在简单看到的倾向Ñ朝向酰胺糖基化-acetylglucosamines，并去除有问题的氢键网络的可能性。在β-而不是α-序列中，N-乙酰基恶唑烷酮直接选择性水解为N-乙酰氨基葡糖可能与氢氧化钡结合使用，该特征归因于乙酰胺羰基与β系列糖苷氧之间形成螯合物。
• Oxazolidinone Protection of <i>N</i>-Acetylglucosamine Confers High Reactivity on the 4-Hydroxy Group in Glycosylation
  作者：David Crich、A. U. Vinod

  DOI：10.1021/ol0342305

  日期：2003.4.1

  [GRAPHICS]The preparation of a convenient oxazolidinone protected N-acetyl glucosamine 4-OH derivative is reported. This substance exhibits enhanced reactivity as a glycosyl acceptor in a variety of coupling methods, the products of which are converted to the target N-acetylglucosaminyl saccharides under very mild conditions.