2-(trimethylsilyl)ethyl 2,6-di-O-benzyl-β-D-galactopyranoside | 177280-23-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(trimethylsilyl)ethyl 2,6-di-O-benzyl-β-D-galactopyranoside
• 英文别名: 2-(trimethylsilyl)ethyl 2,6-di-O-benzyl-beta-d-galactopyranoside；(2R,3R,4S,5R,6R)-5-phenylmethoxy-2-(phenylmethoxymethyl)-6-(2-trimethylsilylethoxy)oxane-3,4-diol
• CAS: 177280-23-8
• 化学式: C₂₅H₃₆O₆Si
• 分子量: 460.643
• InChiKey: YJWBVBHEAYGRKQ-ZLOLNMDISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  32
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl 2,6-di-O-benzyl-β-D-galactopyranoside 在 palladium on activated charcoal 、 palladium hydroxide - carbon 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 Ag-silicate on alumina 、 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三氟乙酸 作用下， 以 吡啶 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 溶剂黄146 为溶剂， -15.0~45.0 ℃ 、17.2 MPa 条件下， 反应 73.25h， 生成 Acetic acid (2R,3R,4S,5S,6R)-3-acetoxy-6-acetoxymethyl-5-((2S,3R,4R,5R,6R)-4,5-diacetoxy-6-acetoxymethyl-3-acetylamino-tetrahydro-pyran-2-yloxy)-2-[16-(toluene-4-sulfonyloxy)-hexadecyloxy]-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  The synthesis of 16-mercaptohexadecanyl glycosides for biosensor applications

  摘要：

  The P-k trisaccharide and the central disaccharide element of asialo GM(1) activated as their trichloroacetimidates were each used to glycosylate 16-(p-toluensulfonyloxy)hexadecanol 1. Displacement of the tosyl group by thiocyanate followed by sodium borohydride reduction and saponification afforded oligosaccharide 16-mercaptohexadecanyl glycosides that were isolated as the corresponding disulfides 6 and 17 unless oxygen was rigorously excluded from the solvents used for work-up. Dithiothreitol reduction of disulfides and subsequent isolation under an inert atmosphere with degassed solvents gave the thiols 7 and 18. Chemisorption of omega-glycosyl alkanethiols and alkanethiols onto gold electrodes produces self-assembled monolayers that can act as amperometric biosensors for the detection of proteins that bind to the immobilized oligosaccharide epitope. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(98)00053-6
• 作为产物：
  描述：

  2-(三甲基硅烷基)乙基beta-吡喃半乳糖苷 在 硫酸 、 sodium hydride 、 N,N-二甲基甲酰胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 26.75h， 生成 2-(trimethylsilyl)ethyl 2,6-di-O-benzyl-β-D-galactopyranoside
  参考文献：
  名称：

  磷酸化半乳糖衍生物的合成及类胰岛素活性

  摘要：

  已进行了分离为钠盐的多磷酸化半乳糖苷6、8、10、13、16和20的合成。分别通过2-（三甲基甲硅烷基）乙基半乳糖苷3和2的糖基化以及随后的完全脱保护来制备非磷酸化的二糖17和三糖21。磷酸化衍生物的初步胰岛素样活性已有报道。

  DOI：

  10.1016/0008-6215(93)84177-8

文献信息

• Syntheses and insulin-like activity of phosphorylated galactose derivatives
  作者：Hugo-Norberto Caro、Manuel Martín-Lomas、Manuel Bernabé

  DOI：10.1016/0008-6215(93)84177-8

  日期：1993.2

  The syntheses of the poly-phosphorylated galactosides 6, 8, 10, 13, 16, and 20, isolated as sodium salts, have been performed. The non-phosphorylated disaccharide 17 and trisaccharide 21 have been prepared via glycosylation of the 2-(trimethylsilyl)ethyl galactosides 3 and 2, respectively, and subsequent complete deprotection. Preliminary insulin-like activity of the phosphorylated derivatives is reported

  已进行了分离为钠盐的多磷酸化半乳糖苷6、8、10、13、16和20的合成。分别通过2-（三甲基甲硅烷基）乙基半乳糖苷3和2的糖基化以及随后的完全脱保护来制备非磷酸化的二糖17和三糖21。磷酸化衍生物的初步胰岛素样活性已有报道。
• A Solution to Chemical Pseudaminylation via a Bimodal Glycosyl Donor for Highly Stereocontrolled α- and β-Glycosylation
  作者：Ruohan Wei、Han Liu、Arthur H. Tang、Richard J. Payne、Xuechen Li

  DOI：10.1021/acs.orglett.9b00990

  日期：2019.5.17

  A robust methodology for the stereocontrolled chemical glycosylation of pseudaminic acid has been developed to afford both α- (axial) and β- (equatorial) glycosides reliably with complete stereoselectivity, using a common glycosyl donor (7N-Cbz/5N-azido Pse thioglycoside) simply by changing the reaction conditions. In the CH2Cl2/MeCN cosolvent, highly β-selective pseudaminylation was observed, while

  已开发出一种可靠的方法对伪氨基酸进行立体控制的化学糖基化反应，可使用常见的糖基供体（7 N -Cbz / 5 N-叠氮基Pse ）可靠地提供α-（轴向）和β-（赤道）糖苷，且具有完全的立体选择性。硫糖苷），只需更改反应条件即可。在CH 2 Cl 2 / MeCN助溶剂中，观察到了高度β-选择性的伪氨基化，而在CH 2 Cl 2中加入5.0当量的DMF则得到了α-伪氨基糖苷。
• Structure-Activity Relationship Study of the Neuritogenic Potential of the Glycan of Starfish Ganglioside LLG-3 ‡
  作者：Megumi Yamagishi、Ritsuko Hosoda-Yabe、Hideki Tamai、Miku Konishi、Akihiro Imamura、Hideharu Ishida、Tomio Yabe、Hiromune Ando、Makoto Kiso

  DOI：10.3390/md13127062

  日期：——

  LLG-3 is a ganglioside isolated from the starfish Linchia laevigata. To clarify the structure-activity relationship of the glycan of LLG-3 toward rat pheochromocytoma PC12 cells in the presence of nerve growth factor, a series of mono- to tetrasaccharide glycan derivatives were chemically synthesized and evaluated in vitro. The methyl group at C8 of the terminal sialic acid residue was crucial for

  LLG-3是从海星Linchia laevigata中分离出来的神经节苷脂。为了阐明在神经生长因子存在下LLG-3聚糖对大鼠嗜铬细胞瘤PC12细胞的构效关系，化学合成了一系列单糖至四糖聚糖衍生物，并在体外进行了评估。末端唾液酸残基C8处的甲基对于神经形成活性至关重要，而末端三糖部分是最小的活性基序。此外，三糖还通过有丝分裂原激活的蛋白激酶（MAPK）信号传导刺激人神经母细胞瘤SH-SY5Y细胞中的神经形成。加入1或10 nM三糖可迅速诱导细胞外信号调节激酶（ERK）1/2的磷酸化。刺激后5分钟，磷酸化ERK与ERK的比例达到最大值，然后逐渐下降。但是，三糖不会诱导明显的Akt磷酸化。这些作用通过用MAPK抑制剂U0126进行预处理而消除，该抑制剂可抑制酶MEK1和MEK2。此外，U0126剂量依赖性地响应于三糖而抑制ERK 1/2的磷酸化。因此，我们得出结论，三糖通过MAPK / ERK信
• Synthesis of building blocks for an iterative approach towards oligomers of the <i>Streptococcus pneumoniae</i> type 1 zwitterionic capsular polysaccharide repeating unit
  作者：Aisling Ní Cheallaigh、Stefan Oscarson

  DOI：10.1139/cjc-2016-0006

  日期：2016.11

  extendable trisaccharide building blocks of the zwitterionic capsular polysaccharides of Spt1 is described. Key elements include the comparison of pre-glycosylation oxidation and post-glycosylation oxidation approaches using thioglycoside donors to the target trisaccharide, the optimisation of the post-glycosylation oxidation approach, and the conversion of the trisaccharide to building blocks tailored

  来自 1 型肺炎链球菌 (Spt1) 的两性离子荚膜多糖提取物，质量约为 8 kDa，已显示出独特的 T 细胞激活特性。Spt1荚膜多糖的三糖重复单元的低聚物[→3)-4-NH2-α-d-QuipNAc-(1→4)-α-d-GalpA-(1→3)-α-d-GalpA- (1-]n 需要定义长度来进一步研究这种反应。描述了一种实现 Spt1 的两性离子荚膜多糖的可迭代扩展的三糖构建块的方法。关键要素包括糖基化前氧化和糖基化后氧化方法的比较使用硫糖苷供体到目标三糖，优化后糖基化氧化方法，以及将三糖转化为为迭代糖基化量身定制的构建块。
• Chemo-Enzymatic Synthesis of Antagonists of the Myelin-associated Glycoprotein (MAG)
  作者：Gan-Pan Gao、Oliver Schwardt、Tamara Visekruna、Said Rabbani、Beat Ernst

  DOI：10.2533/000942904777678019

  日期：——

  Ganglioside GQ1b ? is the most potent antagonist of the Myelin-associated glycoprotein (MAG) identified so far. For the efficient synthesis of the partial structure of GQ1b ? and derivatives thereof, a chemo-enzymatic strategy using the ?(2?3)-sialyltransferase ratST3Gal III (EC 2.4.99.6) was applied. Besides the natural substrates Gal? (1?3)GlcNAc (19) and Gal? (1?4)GlcNAc (20), the disaccharides Gal? (1?3)GalNTCA?-OSE (9), Gal? (1?3)GalNAc?-OSE (11), and Gal? (1?3)Gal?-OSE (14) were also tolerated by the enzyme and were transformed to the target structures in preparative scale.

  GQ1b神经节苷脂是迄今为止发现的髓鞘相关糖蛋白（MAG）中最强效的拮抗剂。为了高效合成GQ1b的部分结构及其衍生物，采用了一种化学-酶联合策略，利用了（2-3）-唾液酸转移酶ratST3Gal III（EC 2.4.99.6）。除了天然底物Gal（1-3）GlcNAc和Gal（1-4）GlcNAc之外，二糖Gal（1-3）GalNTCA- OSE、Gal（1-3）GalNAc- OSE和Gal（1-3）Gal- OSE也被酶耐受，并在制备规模下转化为目标结构。