((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-2-yl)methyl acetate | 143826-39-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-2-yl)methyl acetate
• 英文别名: 6-O-acetyl-2,3,4-tri-O-benzyl-α-D-galactopyranosyl trichloroacetimidate
• CAS: 143826-39-5
• 化学式: C₃₁H₃₂Cl₃NO₇
• 分子量: 636.957
• InChiKey: JTKZXXIVRBLWCL-JYJZCUDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.39
• 重原子数：
  42.0
• 可旋转键数：
  12.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  96.3
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  ((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-2-yl)methyl acetate 在 双(三甲基硫化硅) 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 0.08h， 以79%的产率得到6-O-acetyl-2,3,4-tri-O-benzyl-1-thio-α-D-galactopyranose
  参考文献：
  名称：

  Synthesis of Glycosylthiols and Reactivity Studies

  摘要：

  The acid-catalyzed reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-alpha-D-glucopyranose (7) as glycosyl donor with bis-trimethylsilyl sulfide as acceptor affords the alpha-thiol. Hence, this sterically hindered S-nucleophile as acceptor should provide with O-glycosyl trichloroacetimidates as glycosyl donors that have nonparticipating groups at C-2, glycosylthiols with the thiol group in axial position. This was confirmed for various donors (4, 16-19) with the exception of the corresponding mannosyl donor (20). However, powerful participating groups at C-2 of the donor (23-28) governed the anomeric selectivity.

  DOI：

  10.1021/jo200624e
• 作为产物：
  描述：

  ethyl 6-O-acetyl-2,3,4-tri-O-benzyl-1-thio-β-D-galactopyranoside 在 盐酸 、 N-碘代丁二酰亚胺 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 ((2R,3S,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-(2,2,2-trichloro-1-iminoethoxy)tetrahydro-2H-pyran-2-yl)methyl acetate
  参考文献：
  名称：

  半乳糖构件的糖基化反应过程中的远程参与：低温振动光谱法的直接证据。

  摘要：

  1,2-顺式-糖苷键的立体选择性形成是具有挑战性的。但是，可以通过C4或C6酯基团的远程参与来诱导1,2-顺式选择性。据信涉及远程参与的反应通过关键的离子中间体糖基阳离子进行。尽管许多年前已经提出了机理途径，但由于反应中间体的寿命短，其结构仍然难以捉摸。在这里，我们通过低温振动光谱和第一原理理论揭示参与远程参与反应的糖基阳离子的结构。C4上的乙酰基通过与二恶唑鎓型离子中的异头碳形成共价键，确保α-选择性半乳糖基化。不料，

  DOI：

  10.1002/anie.201916245

文献信息

• Design, Synthesis, and Biological Evaluation of Ganglioside Hp-s1 Analogues Varying at Glucosyl Moiety
  作者：Jung-Tung Hung、Chun-Hong Yeh、Shih-An Yang、Chiu-Ya Lin、Hung-Ju Tai、Ganesh B. Shelke、Daggula Mallikarjuna Reddy、Alice L. Yu、Shun-Yuan Luo

  DOI：10.1021/acschemneuro.6b00069

  日期：2016.8.17

  contributing to the neurogenic activity, we developed feasible procedures for synthesis of Hp-s1 analogues (2a-2f). The glucosyl moiety of Hp-s1 was replaced with alpha-glucose, alpha-galactose, beta-galactose, alpha-mannose, beta-mannose, and their biological activities on SH-SY5Y cells and natural killer T (NKT) cells were evaluated. We found that the orientation of C-2 hydroxyl group at glucosyl moiety

  神经节苷脂Hp-s1分离自海胆Diadema setosum的卵巢。在嗜铬细胞瘤12细胞中，它表现出比GM1更好的神经生成活性。为了探索Hp-s1的葡萄糖基部分在神经活性中的作用，我们开发了合成Hp-s1类似物（2a-2f）的可行程序。用α-葡萄糖，α-半乳糖，β-半乳糖，α-甘露糖，β-甘露糖替换Hp-s1的葡萄糖基部分，并评估它们对SH-SY5Y细胞和自然杀伤T（NKT）细胞的生物学活性。我们发现Hp-s1的葡萄糖基部分的C-2羟基的取向在诱导SH-SY5Y细胞的神经突向外生长中起重要作用。出人意料的是，化合物2d可以激活NKT细胞以产生白介素2，尽管它对SH-SY5Y细胞的神经突生长没有显着活性。
• Stereoselective Organocatalyzed Glycosylation of Glycosyl Trichloroacetimidate Donors: Thiouracil as Brønsted Acid Catalyst
  作者：Ashwani Tiwari、Ariza Khanam、Mohan Lal、Pintu Kumar Mandal

  DOI：10.1002/adsc.202400067

  日期：2024.8.6

  report thiouracil-catalyzed α-selective O-glycosylations employing easily accessible glycosyl trichloroacetimidate donors without using any co-catalyst or additive. A variety of alcohol nucleophiles including saccharides, and amino acids with different protecting groups containing glycosyl trichloroacetimidate donors were successfully α-glycosylated using an operationally simple protocol. Moreover, mechanistic

  在此，我们报道了硫氧嘧啶催化的α-选择性O-糖基化，使用易于获得的糖基三氯乙酰亚胺酯供体，而不使用任何助催化剂或添加剂。使用操作简单的方案成功地将多种醇亲核试剂（包括糖类和具有不同保护基团的含有糖基三氯乙酰亚胺酯供体的氨基酸）进行α-糖基化。此外，机理研究表明硫氧嘧啶在此糖基化过程中起到布朗斯台德酸/碱催化作用。
• First synthesis of a pentasaccharide repeating unit of the O-antigenic polysaccharide from enterohaemorrhagic Escherichia coli O48:H21
  作者：Rajib Panchadhayee、Anup Kumar Misra

  DOI：10.1016/j.tetasy.2009.05.026

  日期：2009.7

  A concise synthesis of a pentasaccharide as its 4-methoxyphenyl glycoside, found in the O-antigenic polysaccharide of enterohaemorrhagic Escherichia coli O48:H21 has been achieved for the first time in excellent yield. Most of the intermediate steps are high yielding and the stereooutcome of each glycosylation step was excellent. Stereoselective glycosylation and removal of the 4-methoxybenzyl group were achieved in one-pot by tuning the reaction conditions. A late-stage TEMPO-mediated oxidation strategy has been adopted for the oxidation of a primary hydroxyl group to carboxylic acid. (C) 2009 Elsevier Ltd. All rights reserved.