1,2,3,4,6-五-O-(三甲基硅烷基)alpha-D-半乳糖 | 32166-80-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 1,2,3,4,6-五-O-(三甲基硅烷基)alpha-D-半乳糖
• 英文名称: 1,2,3,4,6-penta-O-trimethylsilyl-α-D-galactose
• 英文别名: 1,2,3,4,6-pentakis-O-(trimethylsilyl)-α-D-galactopyranose；1,2,3,4,6-penta-O-trimethylsilyl-α-D-galactopyranose；trimethyl-[[(2R,3S,4S,5R,6R)-3,4,5,6-tetrakis(trimethylsilyloxy)oxan-2-yl]methoxy]silane
• CAS: 32166-80-6
• 化学式: C₂₁H₅₂O₆Si₅
• 分子量: 541.068
• InChiKey: PPFHNIVPOLWPCF-XDWAVFMPSA-N

物化性质

• 沸点：
  432.1±45.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)
• 溶解度：
  可溶于氯仿、乙酸乙酯
• 保留指数：
  1892;1906

计算性质

• 辛醇/水分配系数(LogP)：
  6.07
• 重原子数：
  32
• 可旋转键数：
  11
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2,3,4,6-五-O-(三甲基硅烷基)alpha-D-半乳糖 在 碘代三甲硅烷 、 偶氮二甲酸二异丙酯 、 叠氮磷酸二苯酯 、 sodium acetate 、 四丁基碘化铵 、 溶剂黄146 、 N,N-二异丙基乙胺 、 三苯基膦 、 三氟乙酸 、 三甲基膦 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 为溶剂， 反应 10.49h， 生成 1-O-(6-benzureido-6-deoxy-α-D-galactopyranosyl)-2-hexacosylamino-1,3,4-octadecanetriol
  参考文献：
  名称：

  Synthesis of a Versatile Building Block for the Preparation of 6-N-Derivatized α-Galactosyl Ceramides: Rapid Access to Biologically Active Glycolipids

  摘要：

  A concise route to the 6-azido-6-deoxy-alpha-galactosyl-phytosphingosine derivative 9 is reported. Orthogonal protection of the two amino groups allows elaboration of 9 into a range of 6-N-derivatized alpha-galactosyl ceramides by late-stage introduction of the acyl chain of the ceramide and the 6-N-group in the sugar headgroup. Biologically active glycolipids 6 and 8 have been synthesized to illustrate the applicability of the approach.

  DOI：

  10.1021/jo102064p
• 作为产物：
  描述：

  口服葡萄糖 、 六甲基二硅氮烷 在 碘 作用下， 以80%的产率得到1,2,3,4,6-五-O-(三甲基硅烷基)alpha-D-半乳糖
  参考文献：
  名称：

  Highly atom economical uncatalysed and I2-catalysed silylation of phenols, alcohols and carbohydrates, using HMDS under solvent-free reaction conditions (SFRC)

  摘要：

  An uncatalysed silylation of phenols, regardless on the aggregate state and nature of the substituents with 0.55 equiv of HMDS under solvent-free reaction conditions (SFRC) at room temperature is reported. Sterically hindered phenols, carbohydrates and most of the alcohols additionally required a catalytic amount (up to 2 mol%) of iodine. The reaction protocol is very simple; obtaining a pure product, particularly of uncatalysed reactions, was frequently a completely solvent-free process. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2012.03.040

文献信息

• Harnessing the reactivity of poly(methylhydrosiloxane) for the reduction and cyclization of biomass to high-value products
  作者：Nicholas M. Hein、Youngran Seo、Stephen J. Lee、Michel R. Gagné

  DOI：10.1039/c9gc00705a

  日期：——

  Poly(methylhydrosiloxane) (PMHS) has been examined for its ability to reduce and subsequently cyclize carbohydrate substrates using catalytic tris(pentafluorophenyl)borane (BCF). The work herein is the first reported example of the direct conversion of monosaccharides to 1,4-anhydro and 2,5-anhydro products utilizing a hydrosiloxane reducing agent. PMHS is produced from waste products of the silicone

  已对聚（甲基氢硅氧烷）（PMHS）使用催化三（五氟苯基）硼烷（BCF）还原并随后环化碳水化合物底物的能力进行了研究。本文的工作是第一个报道的实例，该实例是利用氢化硅氧烷还原剂将单糖直接转化为1,4-脱水和2,5-脱水的产物。PMHS由有机硅行业的废品生产而成，使其成为传统氢硅烷还原剂的绿色替代品。因此，这项工作有助于实现在精细化学品生产中利用可再生原料的目标。
• Selective Acetylation of Non-anomeric Groups of per-<i>O</i>-Trimethylsilylated Sugars
  作者：Welday Desta Weldu、Cheng-Chung Wang

  DOI：10.1021/acs.joc.0c02813

  日期：2021.4.2

  Selective modification of the hydroxyl groups of sugars has been a long-standing challenge due to their proximate relative reactivity. Herein, we report a TMSOTf-catalyzed selective acetylation of the non-anomeric hydroxyl groups of several per-O-TMS-protected sugar substrates while leaving their anomeric group unaffected. In addition to standing versatile by itself, the anomeric O-TMS group left intact

  糖的羟基的选择性修饰由于其近乎相对的反应性而一直是一个长期的挑战。本文中，我们报道了TMSOTf催化的几种过O -TMS保护的糖底物的非异头羟基的选择性乙酰化，同时不影响其异头基团。除了本身具有通用性之外，可以将完整的异头O -TMS基团官能化，以提供关键的糖前体，如亚氨酸酯供体，否则可以通过逐步的异头脱保护-官能化程序进行合成。
• 4,5-Cis Unsaturated α-GalCer Analogues Distinctly Lead to CD1d-Mediated Th1-Biased NKT Cell Responses
  作者：Yanli Cui、Zhiyuan Li、Zhaodong Cheng、Chengfeng Xia、Yongmin Zhang

  DOI：10.1021/acs.chemrestox.5b00047

  日期：2015.6.15

  The total synthesis of 4,5-cis unsaturated α-GalCer analogues was achieved, and their immune-response altering activity was assessed in vitro as well as in vivo in mice. Using glycosyl iodide as a glycosyl donor, construction of the sphingosine unit was shortened by four steps and single α-stereoselectivity was achieved in good yield (67%). With regard to the therapeutic use of α-GalCer, the novel analogues (1b and 1c) distinctly induced a Th1-biased cytokine response, avoiding induction of a contradictory response and overstimulation.

  4,5-顺式不饱和α-GalCer类似物的全合成得以实现，并评估了它们在体外及小鼠体内的免疫应答改变活性。利用糖基碘作为糖基供体，缩短了鞘氨醇单元的构建步骤，并通过高产率（67%）实现了单一的α-立体选择性。针对α-GalCer的治疗用途，新型类似物（1b和1c）显著诱导了偏向Th1的细胞因子反应，避免了矛盾反应和过度刺激的诱导。
• α-半乳糖神经酰胺新异构体及其合成方法
  申请人：浙江大学

  公开号：CN104497064B

  公开（公告）日：2017-10-24

  本发明提供了一种α‑半乳糖神经酰胺新异构体及其合成方法，在鞘氨醇链的构型改变为4,5顺式双键鞘氨醇链。本发明缩短了反应步骤，提高了收率，省略了一些步骤的后处理和纯化步骤，可用于相似糖神经酰胺的全合成，满足不同的糖神经酰胺的广泛研发应用。
• Synthesis of truncated analogues of the iNKT cell agonist, α-galactosyl ceramide (KRN7000), and their biological evaluation
  作者：Natacha Veerapen、Faye Reddington、Mariolina Salio、Vincenzo Cerundolo、Gurdyal S. Besra

  DOI：10.1016/j.bmc.2010.11.032

  日期：2011.1

  of iNKT cells by α-galactosyl ceramide (α-GalCer), also known as KRN7000, and its truncated analogue OCH induces both Th1- and Th2-cytokines, with OCH inducing a Th2-cytokine bias. Skewing of the iNKT cells’ response towards either a Th1- or Th2-cytokine profile offers potential therapeutic benefits. The length of both the acyl and the sphingosine chains in α-galactosyl ceramides is known to influence

  α-半乳糖基神经酰胺 (α-GalCer)（也称为 KRN7000）及其截短的类似物 OCH对i NKT 细胞的刺激诱导 Th1 和 Th2 细胞因子，而 OCH 诱导 Th2 细胞因子偏向。i NKT细胞对 Th1 或 Th2 细胞因子谱的反应的倾斜提供了潜在的治疗益处。已知 α-半乳糖神经酰胺中的酰基链和鞘氨醇链的长度会影响细胞因子的释放曲线。我们合成了具有截短鞘氨醇链的 α-GalCer 类似物，用于生物学评估，特别强调 Th1/Th2 分布。从常见的前体d-来苏糖开始，鞘氨醇衍生物通过直接的 Wittig 缩合合成。