ethyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside | 399035-89-3

• 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: ethyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside
• 英文别名: ethyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-1-thio-2-trichloroacetamido-β-D-glucopyranoside
• CAS: 399035-89-3
• 化学式: C₂₄H₂₆Cl₃NO₅S
• 分子量: 546.899
• InChiKey: UFEIKOYHJUBAPM-ILHTXMRTSA-N

物化性质

• 熔点：
  203-204 °C
• 沸点：
  660.3±55.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.02
• 重原子数：
  34.0
• 可旋转键数：
  7.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  66.02
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside 在 硼烷四氢呋喃络合物 、 三氟甲磺酸三甲基硅酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 7.0h， 以131 mg的产率得到ethyl 3,4-di-O-benzyl-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  TMSOTf 催化的甲硅烷基化：简化的区域选择性一锅保护和碳水化合物的乙酰化

  摘要：

  已经开发出一种高效的 TMSOTf 催化的 HMDS 糖基硅烷化，它可以很容易地以一锅法与后续反应相结合。其在简化区域选择性一锅法保护和非酶乙酰化方面的应用证明了其有用性。

  DOI：

  10.1002/ejoc.201101267
• 作为产物：
  描述：

  ethyl 2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside 在 camphor-10-sulfonic acid 、 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 4.5h， 生成 ethyl 3-O-benzyl-4,6-O-benzylidene-2-deoxy-2-N-trichloroacetamido-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  Study of glycosylation with N-trichloroacetyl-d-glucosamine derivatives in the syntheses of the spacer-armed pentasaccharides sialyl lacto-N-neotetraose and sialyl lacto-N-tetraose, their fragments, and analogues

  摘要：

  The syntheses of 2-aminoethyl glycosides of the pentasaccharides Neu5Ac-alpha (2 --> 3)-Gal-beta (3(1 --> 4)-GlcNAc-beta (3(1 --> 3)-Gal-beta (1 --> 4)-Glc and Neu5Ac-alpha (2 --> 3)-Gal-beta (1 --> 3)-GlcNAc-beta (1 --> 3)-Gal-beta (1 --> 4)-Glc, their asialo di-, tri-, and tetrasaccharide fragments, and analogues included a systematic study of glycosylation with variously protected mono- and disaccharide donors derived from N-trichloroacetyl-D-glucosamine of galactose, lactose, and lactosamine glycosyl acceptors bearing benzoyl protection around the OH group to be glycosylated. Despite the. low reactivity of these acceptors, stereo specificity and good to excellent yields were obtained with NIS-TfOH-activated thioglycoside donors of such type, or with AgOTf-activated glycosyl bromides, while other promotors, as well as a trichloroacetimidate donor, were less effective, and a beta -acetate donor was inactive. In NIS-TfOH-promoted glycosylation with the thioglycosides, the use of TfOH in catalytic amount led to rapid formation of the corresponding oxazoline, but the quantity of TfOH necessary for further efficient coupling with an acceptor depended on the reactivity of the donor, varying from 0.07 equiv for a 3,6-di-O-benzylated monosaccharide derivative to 2.1 equiv for a peracetylated disaccharide one. In the glycosylation products, the N-trichloroacetyl group was easily converted into N-acetyl by alkaline hydrolysis followed by N-acetylation. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00213-0

文献信息

• The presence of water improves reductive openings of benzylidene acetals with trimethylaminoborane and aluminium chloride
  作者：Andrei A. Sherman、Yuri V. Mironov、Olga N. Yudina、Nikolay E. Nifantiev

  DOI：10.1016/s0008-6215(03)00015-6

  日期：2003.4

  efficient for the reductive openings of the cyclic benzylidene acetals with Me(3)N x BH(3) in tetrahydrofurane than the AlCl(3) alone. Under proposed conditions, the dioxane-type 4,6-O-bezylidene acetals of hexopyranosides give regioselectively the corresponding 4-hydroxy,6-O-benzyl derivatives in excellent yields. Reductive openings of the dioxolane-type 3,4-O-benzylidene acetals of galactopyranoside are

  由无水AlCl（3）和H（2）O以3：1比例原位形成的酸性试剂比四氢呋喃中Me（3）N x BH（3）还原环亚苄基乙缩醛的效率高得多单独的AlCl（3）。在提出的条件下，己吡喃糖苷的二恶烷型4，6-O-亚苄基乙缩醛以优异的产率选择性地给出相应的4-羟基，6-O-苄基衍生物。半乳糖吡喃糖苷的二氧戊环型3,4-O-亚苄基乙缩醛的还原开口也非常有效且具有区域选择性，可生成3-O-苄基衍生物（来自3,4-O-外亚苄基乙缩醛）或4-O-苄基衍生物（来自3,4-O-内-亚苄基缩醛）取决于缩醛碳原子的构型。
• Deoxyfluorination tunes the aggregation of cellulose and chitin oligosaccharides and highlights the role of specific hydroxyl groups in the crystallization process
  作者：Giulio Fittolani、Surusch Djalali、Manishkumar A. Chaube、Theodore Tyrikos-Ergas、Marlene C. S. Dal Colle、Andrea Grafmüller、Peter H. Seeberger、Martina Delbianco

  DOI：10.1039/d2ob01601j

  日期：——

  and pattern) impact the solubility and aggregation of well-defined cellulose and chitin oligomers. While deoxyfluorination increased solubility in water and lowered the crystallinity of cellulose oligomers, chitin was much less affected by the modification. The OH/F substitution also highlighted the role of specific hydroxyl groups in the crystallization process. This work provides guidelines for the

  纤维素和几丁质是丰富的结构多糖，由于它们的结晶性，在大量应用中被大自然利用。化学修饰通常用于调整多糖的物理和机械性能，但会产生异质混合物。因此，这种修饰的效果在分子水平上还不是很清楚。在这项工作中，我们研究了脱氧氟化（位点和模式）如何影响定义明确的纤维素和几丁质低聚物的溶解度和聚集。虽然脱氧氟化增加了在水中的溶解度并降低了纤维素低聚物的结晶度，但几丁质受改性的影响要小得多。OH/F 取代也突出了特定羟基在结晶过程中的作用。这项工作为纤维素和几丁质材料的设计提供了指导。可以想象一种类似的方法来制备能够承受酶促降解的纤维素和几丁质类似物。