trimethylsilyl 2,3 6,2',3',4',6'-hepta-O-trimethylsilyl-α-lactoside | 33428-68-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trimethylsilyl 2,3 6,2',3',4',6'-hepta-O-trimethylsilyl-α-lactoside
• 英文别名: 1,2,3,6,2',3',4',6'-octa-O-trimethylsilyl-α-lactose；α-D-lactose TMS；alpha-Lactose TMS；trimethyl-[[(2R,3S,4S,5R,6S)-3,4,5-tris(trimethylsilyloxy)-6-[(2R,3R,4S,5R,6R)-4,5,6-tris(trimethylsilyloxy)-2-(trimethylsilyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methoxy]silane
• CAS: 33428-68-1
• 化学式: C₃₆H₈₆O₁₁Si₈
• 分子量: 919.756
• InChiKey: QJZFVYJIGWEKIR-IZMYAETLSA-N

物化性质

• 沸点：
  646.8±55.0 °C(Predicted)
• 密度：
  0.98±0.1 g/cm3(Predicted)
• 保留指数：
  2713;2707;2707.6

计算性质

• 辛醇/水分配系数(LogP)：
  9.48
• 重原子数：
  55
• 可旋转键数：
  20
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  102
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  trimethylsilyl 2,3 6,2',3',4',6'-hepta-O-trimethylsilyl-α-lactoside 在 碘代三甲硅烷 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 (((2S,3R,4S,5S,6R)-2-(((2R,3R,4S,5R,6R)-6-iodo-4,5-bis((trimethylsilyl)oxy)-2-(((trimethylsilyl)oxy)methyl)tetrahydro-2H-pyran-3-yl)oxy)-6-(((trimethylsilyl)oxy)methyl)tetrahydro-2H-pyran-3,4,5-triyl)tris(oxy))tris(trimethylsilane)
  参考文献：
  名称：

  Efficient Syntheses of β-Cyanosugars Using Glycosyl Iodides Derived from Per-O-silylated Mono- and Disaccharides

  摘要：

  [GRAPHICS]Reported herein is a general method for the efficient syntheses of a variety of beta -cyano glycosides through the activation of per-O-trimethylsllyl glycosides with TMSI to form alpha -glycosyl iodides, which undergo S(N)2-type displacement when treated with tetrabutylammonium cyanide. The cyanoglycosides were reduced under mild conditions using NaBH4 in the presence of catalytic CoCl2(H2O)(6) in THF/H2O to give the corresponding aminomethyl glycosides.

  DOI：

  10.1021/ol0160405
• 作为产物：
  描述：

  Lactose 、 六甲基二硅氮烷 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 生成 trimethylsilyl 2,3 6,2',3',4',6'-hepta-O-trimethylsilyl-α-lactoside
  参考文献：
  名称：

  Simple one-pot regioselective 6-O-phosphorylation of carbohydrates and trehalose desymmetrization

  摘要：

  生物学上必需的碳水化合物6-磷酸，特别是海藻糖6-磷酸，可以通过涉及最少保护基团操作的两步反应，在优异的整体产率下轻松合成。我们可以裂解二苯基磷酸酯基团以实现进一步的合成目标。

  DOI：

  10.1039/c3cc47180b

文献信息

• 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。
• Novel eco-friendly solution for the regioselective acetylation of per-O-TMS carbohydrates
  作者：Lina Jin、Xianya Mao、Zhikun Wang、Yangyi Mao、Jianwei Mao、Yanli Cui

  DOI：10.1016/j.carres.2020.108074

  日期：2020.9

  Regioselective acetylation of per-O-TMS carbohydrates was achieved preferentially at the 6 position or 1,6-position under mild conditions involving the eco-friendly solvent acetonitrile, at room temperature, in ambient atmosphere and in a shorter time. Good or moderate yields were obtained via 4-dimethylaminopyridine, without auxiliary equipment. A single α-O-Acetyl acetylation anomer was exclusively

  在温和条件下，在环境友好的环境中，在室温，环境气氛中且在较短的时间内，优先在6位或1,6-位上实现per-O-TMS碳水化合物的区域选择性乙酰化。在没有辅助设备的情况下，通过4-二甲基氨基吡啶获得了良好或中等的产率。单独为涉及的底物定义了一个单一的α-O-乙酰乙酰化单体。应用6-O-单乙酸酯衍生物并将其用作二糖构建中的稳定的糖基供体。该方法学成功用于多种底物，包括：d-乳糖，d-海藻糖，d-半乳糖，甲基α-d-半乳糖，d-葡萄糖，d-甘露糖，d-木糖和l-岩藻糖。
• Regioselective 6-detrimethylsilylation of per-O-TMS-protected carbohydrates in the presence of ammonium acetate
  作者：Yanli Cui、Zhaodong Cheng、Jianwei Mao、Yongping Yu

  DOI：10.1016/j.tetlet.2013.05.039

  日期：2013.7

  A convenient methodology has been developed for the regioselective removal of primary trimethylsilyl group (TMS) of various per-O-TMS-protected carbohydrates by inexpensive ammonium acetate. After acetylation and trichloroacetimidation of 6-hydroxyl sugar 1b, other TMS groups of 1d and 1c were inert to ammonium acetate in the same conditions, and this approach was also successfully applied in TMS-protected sphingosine. (C) 2013 Elsevier Ltd. All rights reserved.
• Simple one-pot regioselective 6-O-phosphorylation of carbohydrates and trehalose desymmetrization
  作者：A. Abragam Joseph、Chun-Wei Chang、Cheng-Chung Wang

  DOI：10.1039/c3cc47180b

  日期：——

  Biologically essential carbohydrate 6-phosphates, especially trehalose 6-phosphate, can be synthesized easily in excellent overall yields in 2 steps involving minimum protecting group manipulations. We can cleave the diphenylphosphate group for further synthetic objectives.

  生物学上必需的碳水化合物6-磷酸，特别是海藻糖6-磷酸，可以通过涉及最少保护基团操作的两步反应，在优异的整体产率下轻松合成。我们可以裂解二苯基磷酸酯基团以实现进一步的合成目标。
• Efficient Syntheses of β-Cyanosugars Using Glycosyl Iodides Derived from Per-<i>O</i>-silylated Mono- and Disaccharides
  作者：Abhijit S. Bhat、Jacquelyn Gervay-Hague

  DOI：10.1021/ol0160405

  日期：2001.6.1

  [GRAPHICS]Reported herein is a general method for the efficient syntheses of a variety of beta -cyano glycosides through the activation of per-O-trimethylsllyl glycosides with TMSI to form alpha -glycosyl iodides, which undergo S(N)2-type displacement when treated with tetrabutylammonium cyanide. The cyanoglycosides were reduced under mild conditions using NaBH4 in the presence of catalytic CoCl2(H2O)(6) in THF/H2O to give the corresponding aminomethyl glycosides.