5,6-O-isopropylidene-D-fructose | 148979-55-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-O-isopropylidene-D-fructose
• 英文别名: (3S,4S)-4-[(4R)-2,2-dimethyl-1,3-dioxolan-4-yl]-1,3,4-trihydroxybutan-2-one
• CAS: 148979-55-9
• 化学式: C₉H₁₆O₆
• 分子量: 220.222
• InChiKey: PGECRVKNFCXDOY-BWZBUEFSSA-N

物化性质

• 沸点：
  410.7±40.0 °C(Predicted)
• 密度：
  1.312±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.7
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  96.2
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  5,6-O-isopropylidene-D-fructose 在 氨 、 水 、 碘 、 溶剂黄146 、 三乙胺 、 hydroxylamine-O-sulfonic acid 作用下， 反应 13.5h， 生成 2-Deoxy-D-glucose
  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：

  D-fructose diethyl dithioacetal 在 对甲苯磺酸 、 mercury dichloride 、 mercury(II) oxide 作用下， 以 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 4.0h， 生成 5,6-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

• Biomimetic<i>syn</i>-Aldol Reaction of Dihydroxyacetone Promoted by Water-Compatible Catalysts
  作者：Oskar Popik、Bartosz Zambroń、Jacek Mlynarski

  DOI：10.1002/ejoc.201301436

  日期：2013.11

  The syn-selective direct aldol reaction of unprotected dihydroxyacetone with glyceraldehyde has been catalyzed by serine-based organocatalysts. The application of the catalysts mimics the biosynthesis of ketohexoses in aqueous solvents and leads to fructose and sorbose with excellent diastereoselectivity (up to 95:5 dr). The organocatalytic C3 + C3 methodology presented herein is a versatile direct

  未受保护的二羟基丙酮与甘油醛的顺式选择性直接羟醛反应已由基于丝氨酸的有机催化剂催化。催化剂的应用模拟了己酮糖在水性溶剂中的生物合成，并导致果糖和山梨糖具有出色的非对映选择性（高达 95:5 dr）。本文提出的有机催化 C3 + C3 方法是一种通用的直接进入 D 和 L 系列受保护的同构型糖的方法。
• Amine-Catalyzed Direct Aldol Addition
  作者：Morris Markert、Michael Mulzer、Bernd Schetter、Rainer Mahrwald

  DOI：10.1021/ja071926a

  日期：2007.6.13

  An efficient organo-catalytic, highly syn-stereoselective method for aldol additions between enolizable aldehydes and hydroxyacetone as well as dihydroxyacetone is disclosed. Reactions proceed in the presence of tertiary amines at room temperature. The aldol adducts can be obtained in good to high yields and with high degrees of syn-diastereoselectivity. This new aldol reaction provides an operationally simple protocol for the stereocontrolled synthesis of carbohydrates
• Amine-Catalyzed Direct Aldol Reactions of Hydroxy- and Dihydroxyacetone: Biomimetic Synthesis of Carbohydrates
  作者：Oskar Popik、Monika Pasternak-Suder、Katarzyna Leśniak、Magdalena Jawiczuk、Marcin Górecki、Jadwiga Frelek、Jacek Mlynarski

  DOI：10.1021/jo500860g

  日期：2014.6.20

  This article presents comprehensive studies on the application of primary, secondary, and tertiary amines as efficient organocatalysts for the de novo synthesis of ketoses and deoxyketoses. Mimicking the actions of aldolase enzymes, the synthesis of selected carbohydrates was accomplished in aqueous media by using proline- and serine-based organocatalysts. The presented methodology also provides direct access to unnatural L-carbohydrates from the (S)-glyceraldehyde precursor. Determination of the absolute configuration of all obtained sugars was feasible using a methodology consisting of concerted ECD and VCD spectroscopy.
• 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.