1-deoxy-3,4:5,6-di-O-isopropylidene-D-fructose | 94284-20-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-deoxy-3,4:5,6-di-O-isopropylidene-D-fructose
• 英文别名: 1-deoxy-3,4:5,6-di-O-isopropylidene-D-arabino-hex-2-ulose；1-[(4S,5R)-5-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl]ethanone
• CAS: 94284-20-5
• 化学式: C₁₂H₂₀O₅
• 分子量: 244.288
• InChiKey: CXZICRIDYZTQFN-OPRDCNLKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-deoxy-3,4:5,6-di-O-isopropylidene-D-fructose 在 氨 、 水 、 碘 、 三乙胺 、 三氟乙酸 、 hydroxylamine-O-sulfonic acid 作用下， 反应 6.5h， 生成 1-去氧-D-山梨醇
  参考文献：
  名称：

  Photolysis of 2-azi-2-deoxy-d-arabino-hexitol and analogous hexitols; the ineffectiveness of certain carbohydrate diazirines as photoaffinity labels

  摘要：

  Three diazirines 2-azi-2-deoxy-D-arabino-hexitol (4), its 1-deoxy analogue (5), and 3-azi-3,6-dideoxy-L-xylo-hexitol (9) were synthesised and their products of photolysis analysed by TLC. Diazirine 4 gave exclusively 2-deoxy-D-arabino-hexose (12), 5 gave predominantly 1,2-dideoxy-D-erythro-3-hexulose (10) and 1-deoxy-D-glucitol (11), and 9 did not yield any main product. Carrying out the irradiation of 4 in D2O gave selectively (2S)-2-deoxy-D-arabino-(2-H-2)hexose (12a). The results indicate that photolysis of a diazirine flanked by a hydroxymethyl group, as in compound 4, leads to a rapid and stereoselective intramolecular reaction of the intermediate. This may be an explanation of why compound 4 is ineffective as a photoaffinity reagent for mannitol permease (D-mannitol-specific enzyme II) of the E. coli phosphotransferase system for which it is a substrate. A secondary hydroxymethylene group has a less pronounced effect and still allows some reaction with the medium.

  DOI：

  10.1016/0008-6215(93)84209-o
• 作为产物：
  描述：

  3,4:5,6-di-O-isopropylidene-D-glucose diethyl dithioacetal 在 磷酸 、 4 A molecular sieve 、 镍 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二甲基亚砜 为溶剂， 反应 18.0h， 生成 1-deoxy-3,4:5,6-di-O-isopropylidene-D-fructose
  参考文献：
  名称：

  Photolysis of 2-azi-2-deoxy-d-arabino-hexitol and analogous hexitols; the ineffectiveness of certain carbohydrate diazirines as photoaffinity labels

  摘要：

  Three diazirines 2-azi-2-deoxy-D-arabino-hexitol (4), its 1-deoxy analogue (5), and 3-azi-3,6-dideoxy-L-xylo-hexitol (9) were synthesised and their products of photolysis analysed by TLC. Diazirine 4 gave exclusively 2-deoxy-D-arabino-hexose (12), 5 gave predominantly 1,2-dideoxy-D-erythro-3-hexulose (10) and 1-deoxy-D-glucitol (11), and 9 did not yield any main product. Carrying out the irradiation of 4 in D2O gave selectively (2S)-2-deoxy-D-arabino-(2-H-2)hexose (12a). The results indicate that photolysis of a diazirine flanked by a hydroxymethyl group, as in compound 4, leads to a rapid and stereoselective intramolecular reaction of the intermediate. This may be an explanation of why compound 4 is ineffective as a photoaffinity reagent for mannitol permease (D-mannitol-specific enzyme II) of the E. coli phosphotransferase system for which it is a substrate. A secondary hydroxymethylene group has a less pronounced effect and still allows some reaction with the medium.

  DOI：

  10.1016/0008-6215(93)84209-o

文献信息

• Synthesis of Acyclic <i>C</i>‐Nucleoside Analogues Using (<i>E</i>)‐1,2‐Dideoxy‐1‐dimethylamino‐4,5:6,7‐di‐<i>O</i>‐isopropylidene‐<scp>d</scp>‐<i>arabino</i>‐hept‐1‐en‐3‐ulose
  作者：Karen Methling、Jürgen Kopf、Manfred Michalik、Helmut Reinke、Christiane Bürger、Heiderose Oberender、Klaus Peseke

  DOI：10.1081/car-120026457

  日期：2003.12.31

  1-Deoxy-3,4:5,6-di-O-isopropylidene-D-arabino-hex-2-ulose reacted with N,N-dimethylformamide dimethyl acetal and tert-butoxy [bis(dimethylamino)] methane, respectively, to furnish (E)-1,2-dideoxy-1-dimethylamino-4,5:6,7-di-O-isopropylidene-D-arabino-hept-1-en-3-ulose. This push-pull activated heptenulose underwent ring closure reactions with various N,N'-nucleophiles like hydrazine hydrate, amidinium, guanidinium and isothiouronium salts in the presence of bases to yield pyrazole and pyrimidine derivatives, respectively, all of which derivatized with a di-O-isopropylidenated tetritol side chain. The isopropylidene groups were removed with methanolic HCl in the pyrazole series, whereas aq TFA was used in the case of pyrimidine analogues.
• Photolysis of 2-azi-2-deoxy-d-arabino-hexitol and analogous hexitols; the ineffectiveness of certain carbohydrate diazirines as photoaffinity labels
  作者：Jochen Lehmann、Stefan Petry

  DOI：10.1016/0008-6215(93)84209-o

  日期：1993.2

  Three diazirines 2-azi-2-deoxy-D-arabino-hexitol (4), its 1-deoxy analogue (5), and 3-azi-3,6-dideoxy-L-xylo-hexitol (9) were synthesised and their products of photolysis analysed by TLC. Diazirine 4 gave exclusively 2-deoxy-D-arabino-hexose (12), 5 gave predominantly 1,2-dideoxy-D-erythro-3-hexulose (10) and 1-deoxy-D-glucitol (11), and 9 did not yield any main product. Carrying out the irradiation of 4 in D2O gave selectively (2S)-2-deoxy-D-arabino-(2-H-2)hexose (12a). The results indicate that photolysis of a diazirine flanked by a hydroxymethyl group, as in compound 4, leads to a rapid and stereoselective intramolecular reaction of the intermediate. This may be an explanation of why compound 4 is ineffective as a photoaffinity reagent for mannitol permease (D-mannitol-specific enzyme II) of the E. coli phosphotransferase system for which it is a substrate. A secondary hydroxymethylene group has a less pronounced effect and still allows some reaction with the medium.