2-(trimethylsilyl)ethyl-4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside | 1246852-08-3

• 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: 2-(trimethylsilyl)ethyl-4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside
• 英文别名: 2,2,2-trichloroethyl N-[(2R,4aR,6R,7R,8R,8aS)-8-hydroxy-2-phenyl-6-(2-trimethylsilylethoxy)-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-yl]carbamate
• CAS: 1246852-08-3
• 化学式: C₂₁H₃₀Cl₃NO₇Si
• 分子量: 542.916
• InChiKey: ZEHULBZPRJWHMW-MGYGNFHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.01
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  95.5
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl-4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside 在 溶剂黄146 、 锌 作用下， 以99%的产率得到(2R,4aR,6R,7R,8R,8aS)-7-amino-2-phenyl-6-(2-(trimethylsilyl)ethoxy)hexahydropyrano[3,2-d][1,3]dioxin-8-ol
  参考文献：
  名称：

  Syntheses of 2-NBDG analogues for monitoring stereoselective uptake of d -glucose

  摘要：

  2-NBDG is a widely used fluorescent tracer for monitoring D-glucose uptake into single living cells. However, 2-NBDG alone is not sufficient for monitoring the net stereoselective uptake of D-glucose, unless its possible non-stereoselective uptake is properly evaluated. L-Glucose derivatives, which emit fluorescence distinct from that of 2-NBDG, should provide valuable information on the stereoselective uptake, when used with 2-NBDG in combination. In the present study, we synthesized Texas Red (sulforhodamine 101 acid)-coupled and [2-(benz-2-oxa-1,3-diazol-4-yl)amino]-coupled 2-deoxy-D-glucose, referred to as [2-TRG] and [2-BDG], respectively. These derivatives showed emission wavelength longer and shorter than that of 2-NBDG, respectively. 2-TRLG, an antipode of 2-TRG, proved to be an effective tracer for evaluating the extent of non-stereoselective uptake of 2-NBDG when used simultaneously with 2-NBDG. On the other hand, 2-BDG exhibited very weak fluorescence, but the application of a novel cross coupling in the presence of a benzoxadiazole group may be useful for the future development of effective glucose tracers. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2011.04.148
• 作为产物：
  描述：

  2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-D-glucopyranose 在 吡啶 、 2,4,6-三甲基吡啶 、 甲醇 、 氢溴酸 、 sodium methylate 、 silver trifluoromethanesulfonate 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 2-(trimethylsilyl)ethyl-4,6-O-benzylidene-2-deoxy-2-(2,2,2-trichloroethoxycarbonylamino)-β-D-glucopyranoside
  参考文献：
  名称：

  Syntheses of 2-NBDG analogues for monitoring stereoselective uptake of d -glucose

  摘要：

  2-NBDG is a widely used fluorescent tracer for monitoring D-glucose uptake into single living cells. However, 2-NBDG alone is not sufficient for monitoring the net stereoselective uptake of D-glucose, unless its possible non-stereoselective uptake is properly evaluated. L-Glucose derivatives, which emit fluorescence distinct from that of 2-NBDG, should provide valuable information on the stereoselective uptake, when used with 2-NBDG in combination. In the present study, we synthesized Texas Red (sulforhodamine 101 acid)-coupled and [2-(benz-2-oxa-1,3-diazol-4-yl)amino]-coupled 2-deoxy-D-glucose, referred to as [2-TRG] and [2-BDG], respectively. These derivatives showed emission wavelength longer and shorter than that of 2-NBDG, respectively. 2-TRLG, an antipode of 2-TRG, proved to be an effective tracer for evaluating the extent of non-stereoselective uptake of 2-NBDG when used simultaneously with 2-NBDG. On the other hand, 2-BDG exhibited very weak fluorescence, but the application of a novel cross coupling in the presence of a benzoxadiazole group may be useful for the future development of effective glucose tracers. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmcl.2011.04.148

文献信息

• Indirect synthetic route to α-<scp>l</scp>-fucosides <i>via</i> highly stereoselective construction of α-<scp>l</scp>-galactosides followed by C6-deoxygenation
  作者：Hirotaka Tomida、Takuya Matsuhashi、Hide-Nori Tanaka、Naoko Komura、Hiromune Ando、Akihiro Imamura、Hideharu Ishida

  DOI：10.1039/d0ob01128b

  日期：——

  We developed an indirect synthetic method for α-L-fucosides. Based on the fact that L-fucose is 6-deoxy-L-galactose, our strategy consists of the stereoselective construction of α-L-galactoside and its conversion to α-L-fucoside via C6-deoxygenation. The formation of α-L-galactoside is strongly directed using 4,6-O-di-tert-butylsilylene(DTBS)-protected L-galactosyl donors. The DTBS-directed α-L-galactosylation

  我们开发了一种α- L-岩藻糖苷的间接合成方法。基于L-岩藻糖为6-脱氧-L-半乳糖的事实，我们的策略包括立体选择性地构建α- L-半乳糖苷并通过C6-脱氧将其转化为α - L-岩藻糖苷。α-形成大号半乳糖苷是使用4,6-强烈定向ø -二-叔-butylsilylene（DTBS）保护的大号半乳糖供体。DTBS定向的α- L-半乳糖基化显示出广泛的底物适用性，以及出色的偶联收率和α-选择性。在α- L的C6-脱氧中-半乳糖苷，Barton-McCombie反应促进了向L-岩藻糖苷的高产率转化。为了证明我们方法的适用性，我们合成了天然存在的α- L-岩藻糖苷。
• Synthesis, Inhibitory Effects on Nitric Oxide and Structure-Activity Relationships of a Glycosphingolipid from the Marine Sponge Aplysinella rhax and Its Analogues
  作者：Yuzo Fujita、Naohiro Ohshima、Ai Hasegawa、Frank Schweizer、Tadahiro Takeda、Fumiyuki Kiuchi、Noriyasu Hada

  DOI：10.3390/molecules16010637

  日期：——

  The novel glycosphingolipid, b-D-GalNAcp(1®4)[a-D-Fucp(1®3)]-b-D-GlcNAcp(1®)Cer (A), isolated from the marine sponge Aplysinella rhax has a unique structure, with D-fucose and N-acetyl-D-galactosamine moieties attached to a reducing-end N-acetyl-D-glucosamine through an a1®3 and b1®4 linkage, respectively. We synthesized glycolipid 1 and some non-natural di- and trisaccharide analogues 2-6 containing a D-fucose residue. Among these compounds, the natural type showed the most potent nitric oxide (NO) production inhibitory activity against LPS-induced J774.1 cells. Our results indicate that both the presence of a D-Fuca1-3GlcNAc-linkage and the ceramide aglycon portion are crucial for optimal NO inhibition.

  从海洋海绵 Aplysinella rhax 中分离出的新型糖磷脂--b-D-GalNAcp(1®4)[a-D-Fucp(1®3)]-b-D-GlcNAcp(1®)Cer (A) 具有独特的结构，D-岩藻糖和 N-乙酰基-D-半乳糖胺分别通过 a1®3 和 b1®4 连接到还原端的 N-乙酰基-D-葡萄糖胺上。我们合成了糖脂 1 和一些含有 D-岩藻糖残基的非天然二糖和三糖类似物 2-6。在这些化合物中，天然型糖脂对 LPS 诱导的 J774.1 细胞一氧化氮（NO）产生的抑制活性最强。我们的研究结果表明，D-Fuca1-3GlcNAc 连接和神经酰胺苷元部分的存在对于达到最佳的一氧化氮抑制效果至关重要。
• Synthesis of structurally-defined polymeric glycosylated phosphoprenols as potential lipopolysaccharide biosynthetic probes
  作者：Lei Wang、Todd L. Lowary

  DOI：10.1039/d1sc03852d

  日期：——

  to study LPS biosynthetic pathways have consisted primarily of small fragments of the larger structure (e.g., the O-chain repeating unit). While such compounds have helped to provide significant insight into many aspects of LPS assembly, understanding other aspects will require larger, more complex probes. For example, the molecular interactions between polymeric LPS biosynthetic intermediates and

  脂多糖 (LPS) 是革兰氏阴性菌产生的关键免疫调节分子，其生物合成一直是一个长期关注的话题。迄今为止，用作研究 LPS 生物合成途径的工具的化学探针主要由较大结构的小片段组成（例如，O 链重复单元）。虽然此类化合物有助于深入了解 LPS 组装的许多方面，但了解其他方面需要更大、更复杂的探针。例如，聚合 LPS 生物合成中间体与将它们穿过内膜和外膜的蛋白质之间的分子相互作用在很大程度上仍然未知。我们描述了两种脂联多糖的合成，其中包含 11 和 27 个单糖残基，它们与大肠杆菌O9a 中的LPS O 链生物合成有关。这项工作不仅导致了数毫克数量的两种生物合成探针，而且还提供了对结构定义多糖的化学合成中必须克服的挑战的见解。