1,2-O-isopropylidene-3,4-O-(o-xylylene)-β-D-fructopyranose | 905715-43-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,2-O-isopropylidene-3,4-O-(o-xylylene)-β-D-fructopyranose
• 英文别名: (4S,4'R,4'aR,12'aS)-2,2-dimethylspiro[1,3-dioxolane-4,1'-3,4,4a,6,11,12a-hexahydropyrano[3,4-c][2,5]benzodioxocine]-4'-ol
• CAS: 905715-43-7
• 化学式: C₁₇H₂₂O₆
• 分子量: 322.358
• InChiKey: ZNYLSVHAJPZYNN-AIANPOQGSA-N

物化性质

• 沸点：
  492.4±45.0 °C(Predicted)
• 密度：
  1.31±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  23
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1,2-O-isopropylidene-3,4-O-(o-xylylene)-β-D-fructopyranose 在 palladium on activated charcoal 吡啶 、 盐酸 、 sodium azide 、 氢气 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， -25.0~20.0 ℃ 、400.0 kPa 条件下， 反应 3.5h， 生成 2,5-二(羟基甲基)-3,4-吡咯烷二醇
  参考文献：
  名称：

  Intramolecular Benzyl Protection Delivery:  A Practical Synthesis of DMDP and DGDP from d-Fructose

  摘要：

  A two-step protection of 1,2-diols as the corresponding o-xylylene cyclic ethers, involving an intramolecular ring-closing O-benzylation reaction, has been developed to overcome the problems associated to regioselective benzylation reactions. The strategy has been applied to the high-yielding synthesis of the pyrrolidine glycosidase inhibitors DMDP and DGDP.

  DOI：

  10.1021/ol052668u
• 作为产物：
  描述：

  1,2-二(溴甲基)苯 在 sodium hydride 、 溶剂黄146 作用下， 以 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.58h， 生成 1,2-O-isopropylidene-3,4-O-(o-xylylene)-β-D-fructopyranose
  参考文献：
  名称：

  Intramolecular Benzyl Protection Delivery:  A Practical Synthesis of DMDP and DGDP from d-Fructose

  摘要：

  A two-step protection of 1,2-diols as the corresponding o-xylylene cyclic ethers, involving an intramolecular ring-closing O-benzylation reaction, has been developed to overcome the problems associated to regioselective benzylation reactions. The strategy has been applied to the high-yielding synthesis of the pyrrolidine glycosidase inhibitors DMDP and DGDP.

  DOI：

  10.1021/ol052668u

文献信息

• Stereoselective Synthesis of Difructose Dianhydrides by Use of the Xylylene Group as Stereodirecting Element in Spiroketalisation Reactions
  作者：Alejandro Méndez-Ardoy、Elena Suárez-Pereira、Patricia Balbuena Oliva、José Luis Jiménez Blanco、Carmen Ortiz Mellet、José M. García Fernández

  DOI：10.1002/ejoc.201000946

  日期：2011.1

  This work was financially supported by the Spanish Ministerio de Ciencia e Innovacion (contract numbers CTQ2006-15515-C02-01/BQU, CTQ2007-61180/PPQ) and the Junta de Andalucia. A. M.-A. is an FPU fellow. E. S.-P. is a “Project of Excellence” fellow (Junta de Andalucia, Ref: P06AGR-02150).

  这项工作得到了西班牙部长级 Ciencia e Innovacion（合同编号 CTQ2006-15515-C02-01/BQU、CTQ2007-61180/PPQ）和安达卢西亚军政府的财政支持。AM-A。是 FPU 研究员。ES-P。是“卓越项目”研究员（安达卢西亚军政府，编号：P06AGR-02150）。
• The o-xylylene protecting group as an element of conformational control of remote stereochemistry in the synthesis of spiroketals
  作者：Patricia Balbuena、Enrique M. Rubio、Carmen Ortiz Mellet、José M. García Fernández

  DOI：10.1039/b604718a

  日期：——

  Protection of trans-1,2-diol segments as cyclic o-xylylene ethers strongly favours diequatorial over diaxial dispositions; the possibility of using this grouping for remote control of the stereochemistry in the synthesis of spiroketals is here demonstrated by the stereoselective synthesis of tricyclic spirodisaccharides (di-D-fructose dianhydrides).

  作为环状 o-xylylene 醚的 trans-1,2-二醇片段的保护，强烈倾向于选择双赤平面而非双轴态；通过对三环脊糖（双 D-果糖二酐）的立体选择性合成，展示了利用该基团在脊酮合成中对立体化学进行远程控制的可能性。
• Stereoselective synthesis of nonsymmetrical difructose dianhydrides from xylylene-tethered d-fructose precursors
  作者：Farida Louis、M. Isabel García-Moreno、Patricia Balbuena、Carmen Ortiz Mellet、José M. García Fernández

  DOI：10.1016/j.tet.2008.01.054

  日期：2008.3

  Nonsymmetrical furanose-pyranose difructose dianhydrides (DFAs), a class of cyclic disaccharides present in foodstuffs, have been prepared in high yield by connecting the reacting monosaccharide moieties through a xylylene bridge prior to triflic acid-promoted bis-spiroketalization. The reaction can then proceed either intra- or intermolecularly, both the regio- and the stereoselectivity being strongly dependent on the spacer length. Noteworthy, the longer m- and p-xylylene positional isomers led to the thermodynamic alpha-D-fructofuranose beta-D-fructopyranose 1,2':2,1'-dyanhydride 1, the major DFA in commercial caramel, in a stereoselective manner. The shorter o-xylylene tether afforded preferentially the elusive contra-thermodynamic beta-D-fructofuranose alpha-D-fructopyranose diastereomer 2, a trace constituent of caramel. The results have been rationalized in terms of stereoelectronic and conformational properties and offer new perspectives for the preparation of pure DFA standards for analytical and nutritional studies. (C) 2008 Elsevier Ltd. All rights reserved.