3,4-O-isopropylidene-6-O-tert-butyldimethylsilyl-1-allyl-α-D-talopyranoside | 1010796-89-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4-O-isopropylidene-6-O-tert-butyldimethylsilyl-1-allyl-α-D-talopyranoside
• CAS: 1010796-89-0
• 化学式: C₁₈H₃₄O₅Si
• 分子量: 358.55
• InChiKey: RCEIUQINOIWNPO-DGXTUMSLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  24.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  57.15
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  3,4-O-isopropylidene-6-O-tert-butyldimethylsilyl-1-allyl-α-D-talopyranoside 在 溶剂黄146 作用下， 以 水 为溶剂， 以90%的产率得到1-(α-D-talopyranosyl)-2-propene
  参考文献：
  名称：

  Hydration IndexA Better Parameter for Explaining Small Molecule Hydration in Inhibition of Ice Recrystallization

  摘要：

  Several simple mono- and disaccharides have been assessed for their ability to inhibit ice recrystallization. Two carbohydrates were found to be effective recrystallization inhibitors. D-Galactose (1) was the best monosaccharide and D-melibiose (5) was the most active disaccharide. The ability of each carbohydrate to inhibit ice growth was correlated to its respective hydration number reported in the literature. A hydration number reflects the number of tightly bound water molecules to the carbohydrate and is a function of carbohydrate stereochemistry. It was discovered that using the absolute hydration number of a carbohydrate does not allow one to accurately predict its ability to inhibit ice recrystallization. Consequently, we have defined a hydration index in which the hydration number is divided by the molar volume of the carbohydrate. This new parameter not only takes into account the number of water molecules tightly bound to a carbohydrate but also the size or volume of a particular solute and ultimately the concentration of hydrated water molecules. The hydration index of both mono- and disaccharides correlates well with experimentally measured RI activity. C-Linked derivatives of the monosaccharides appear to have RI activity comparable to that of their O-linked saccharides but a more thorough investigation is required. The relationship between carbohydrate concentration and RI activity was shown to be noncolligative and a 0.022 M solution of D-galactose (1) and C-linked galactose derivative (10) inhibited recrystallization as well as a 3% DMSO solution. The carbohydrates examined in this study did not possess any thermal hysteresis activity (selective depression of freezing point relative to melting point) or dynamic ice shaping. As such, we propose that they are inhibiting recrystallization at the interface between bulk water and the quasi liquid layer (a semiordered interface between ice and bulk water) by disrupting the preordering of water.

  DOI：

  10.1021/ja806284x
• 作为产物：
  描述：

  在 sodium tetrahydroborate 作用下， 以 甲醇 为溶剂， 以0.41 g的产率得到3,4-O-isopropylidene-6-O-tert-butyldimethylsilyl-1-allyl-α-D-talopyranoside
  参考文献：
  名称：

  The Importance of Hydration for Inhibiting Ice Recrystallization with C-Linked Antifreeze Glycoproteins

  摘要：

  The role of hydration in modulating solution conformation, molecular recognition, and biological activity of oligosaccharides, proteins, and nucleotides is widely recognized but is often neglected when investigating many biological processes such as the mechanism by which biological antifreezes inhibit the growth of ice. We have investigated the relationship between carbohydrate configuration and recrystallization-inhibition (RI) activity in functional C-linked antifreeze glycoprotein (AFGP) analogues using a series of analogues 1-4. While analogues 1-4 did not show any thermal hysteresis (TH) activity, 1 did exhibit weak dynamic ice shaping indicating that this compound had the ability to interact with the ice lattice. The D-mannose and D-talose analogues (3 and 4, respectively) exhibited very weak RI activity with mean largest grain size values similar to phosphate buffered saline, the negative control. D-Glucose analogue 2 exhibited moderate RI activity while D-galactose analogue 1 was the most potent analogue with RI activity comparable to the native AFGP 8. These results suggest that the configuration of the carbohydrate moiety in C-linked AFGP analogues is extremely important and modulates recrystallization-inhibition activity. It seems likely that differences in hydration for each C-linked pyranose alter the compatibility of the carbohydrate moiety with the three-dimensional hydrogen-bonded network of supercooled bulk water. Consequently, the energy associated with transferring a water molecule to the ice lattice changes and can result in inhibition of ice growth. These results emphasize the importance of continued studies to further elucidate the role of hydration in antifreeze activity.

  DOI：

  10.1021/ja7103262