D-xylo-hexos-5-ulose | 19684-22-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: D-xylo-hexos-5-ulose
• 英文别名: (2R,3R,4S)-2,3,4,6-tetrahydroxy-5-oxohexanal
• CAS: 19684-22-1
• 化学式: C₆H₁₀O₆
• 分子量: 178.142
• InChiKey: ZAVYLQGLQYIKKF-OTWZMJIISA-N

物化性质

• 沸点：
  425.4±40.0 °C(Predicted)
• 密度：
  1.574±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -3.1
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  115
• 氢给体数：
  4
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  D-xylo-hexos-5-ulose 在 palladium dihydroxide 氢气 、 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 生成 1-脱氧野尻霉素
  参考文献：
  名称：

  一步法从二羰基糖中制得吡咯烷和哌啶氨基糖。1-deoxynojirimycin的简捷合成

  摘要：

  二羰基糖是通过双重还原胺化反应（NaCNBH 3，MeOH）进行立体选择性合成羟基化哌啶和吡咯烷的便​​利底物。使用这种策略，由5-酮-D-果糖（2，可商购）和5-酮-D-葡萄糖（2，5-脱水亚氨基-D-葡萄糖醇（1）和1-脱氧野rim霉素（3））制备。4）。

  DOI：

  10.1016/s0040-4039(00)97169-7
• 作为产物：
  描述：

  1,2-O-异亚丙基-D-呋喃葡萄糖 在 Dowex 50W-X₈ 、 溴 、 二正丁基氧化锡 作用下， 以 水 为溶剂， 反应 37.67h， 生成 D-xylo-hexos-5-ulose
  参考文献：
  名称：

  Expeditious Synthesis of Aza sugars by the Double Reductive Amination of Dicarbonyl Sugars

  摘要：

  Polyhydroxylated pyrrolidines and piperidines were prepared by the double reductive amination of dicarbonyl, sugars with primary amines and NaCNBH3 in MeOH. Stereocontrol in these reactions depended on the nature of the amine and dicarbonyl sugar. For example, 5-keto-D-fructose (7) gave three pyrrolidine stereoisomers, with the N-alkylated 2,5-anhydro-2,5-imino-D-glucitol predominating. Under similar reaction conditions with benzhydrylamine, 5-keto-D-glucose (20) afforded a 96:4 mixture of piperidines favoring D-gluco 25A, whereas 5-keto-D-mannose (6) produced a 67:33 mixture enriched in D-manno isomer 40. This method allowed for the direct and relatively short synthesis of 1-deoxynojirimycin (DNJ, 1) and 1-deoxymannojirimycin (DMJ, 5) and N-alkylated derivatives thereof. Similar reactions with O-protected 5-keto-D-glucose derivatives 21 and 22 were less stereoselective and lower yielding.

  DOI：

  10.1021/jo00090a040

文献信息

• Iminosugar glycoconjugates
  申请人：Technische Universität Graz

  公开号：EP1903034A1

  公开（公告）日：2008-03-26

  The iminosugar conjugates according to the invention are N-alkylated 1,5-dideoxy-1,5-iminohexitol or 1,5-dideoxy-1,5-iminopentitol derivatives. The iminosugar component can be, for example, D-gluco-, L-ido-, D-galacto-, D-manno-, 2-acetamido-2-deoxy-D-gluco- or xylo-configuration. The N-substituent is a protected L-α-aminoacid derivative, showing L-lysine-like structural features. The linkage between the carbohydrate and the peptide component is not via the usual glycosidic position, but shows structural features of a very stable tertiary amine. Thus the linkage is very stable. These new compounds are synthesised by using catalytic intramolecular reductive amination of dicarbonyl sugars with partially protected amino acids. The process of intramolecular reductive amination itself is carried out using Pearlman's catalyst (Pd(OH)2/C) and H2 at ambient pressure and room temperature. The resulting accessible class of iminosugar conjugate compounds is represented by the general structure shown in Figure 4(c). The alkyl chain length parameter n can be freely chosen from n=0 upwards. Preferably n is between 0 and 10, and more preferably n is 2, 3, or 4. Residue R1 can be chosen from H, OH, or NHAc, with Ac being Acetyl. R2 can be H, OH, or NHAc. R3, R4, R5, R6 can be H or OH. R7 and R8 can be H, CH2OH CH3, COQH, or COOR with R being Alkyl or Aryl. R9 and R10 can be chosen from H, NH2, NHR, with R being a protective group, an amino acid, a peptide, or a protein. R11 can be OH, O-Alkyl, O-Aryl, NH2, N-Alkyl, N-Aryl, amino acid or peptide, connected via an amide bond.

  本发明涉及的亚氨基糖缀合物是N-烷基化的1,5-二脱氧-1,5-亚氨基己糖醇或1,5-二脱氧-1,5-亚氨基戊糖醇衍生物。亚氨基糖部分可以是例如D-葡萄糖、L-艾杜糖、D-半乳糖、D-甘露糖、2-乙酰氨基-2-脱氧-D-葡萄糖或木糖构型。N-取代基是一种保护的L-α-氨基酸衍生物，显示出类似L-赖氨酸的结构特征。糖和肽组分之间的连接不是通过常规的糖苷位置，而是显示出非常稳定的叔胺的结构特征。因此，这种连接非常稳定。这些新化合物是通过使用催化剂催化二羰基糖与部分保护的氨基酸之间的分子内还原胺化合成的。分子内还原胺化过程本身是在常压和室温下使用Pearlman催化剂（Pd(OH)2/C）和氢气进行的。由此得到的一类亚氨基糖缀合物化合物的可及性由图4(c)所示的通用结构表示。烷基链长参数n可以从n=0开始自由选择。优选n在0到10之间，更优选n为2、3或4。残基R1可以从H、OH或NHAc中选择，其中Ac代表乙酰基。R2可以是H、OH或NHAc。R3、R4、R5、R6可以是H或OH。R7和R8可以是H、CH2OH、CH3、COQH或COOR，其中R是烷基或芳基。R9和R10可以从H、NH2、NHR中选择，其中R是一个保护基团、氨基酸、肽或蛋白质。R11可以是OH、O-烷基、O-芳基、NH2、N-烷基、N-芳基、氨基酸或肽，通过酰胺键连接。
• Synthesis of <scp>d</scp>-Hexos-5-uloses by Novel in Situ Hydrolysis of Epoxides Derived from 6-Deoxyhex-5-enopyranosides
  作者：Philomena M. Enright、Kathy M. O'Boyle、Paul V. Murphy

  DOI：10.1021/ol006714w

  日期：2000.11.1

  see text] Epoxides derived from 2,3, 4-tri-O-protected-6-deoxyhex-5-enopyranosides are hydrolyzed in situ to ultimately give novel protected-D-hexos-5-ulose derivatives (sugar 1,5-dicarbonyls, 5-ketohexoses) in moderate to high yields. The products adopt a bicyclic structure (1,6-anhydropyranos-5-ulose) in solution with the pyranose ring in (4)C(1) conformation. The methodology has been used to prepare

  [反应：请参阅文字]由2,3，4-三-O-保护的6-脱氧己基-5-烯吡喃糖苷衍生而来的环氧化物原位水解，最终得到新颖的保护的D-己糖5-蔗糖衍生物（糖1， 5-二羰基，5-酮己糖），产量中等至高。该产物在溶液中采用双环结构（1,6-脱水吡喃-5--5-糖），吡喃糖环呈（4）C（1）构型。该方法已用于制备D-木酮己糖5-蔗糖（5-酮葡萄糖），1-脱氧野oji霉素的合成前体以及肌醇生物合成中的可能中间体。
• A Study of the Epoxidation of 6-Deoxyhex-5-enopyranosides. 1,5-Dicarbonyl Derivatives and Novel Synthetic Routes to <scp>d</scp>-<i>xylo</i>-Hexos-5-ulose and <scp>d</scp>-<i>lyxo</i>-Hexos-5-ulose
  作者：Philomena M. Enright、Manuela Tosin、Mark Nieuwenhuyzen、Linda Cronin、Paul V. Murphy

  DOI：10.1021/jo016378c

  日期：2002.5.1

  s and preliminary exploration of their synthetic potential. Prolonged epoxidation reaction times led to their hydrolysis in situ and gave novel protected D-hexos-5-ulose derivatives (sugar 1,5-dicarbonyls). Some reactions of the hexos-5-uloses were studied, and in some cases septanoside (seven-membered-ring saccharide) derivatives were isolated. Novel routes to D-xylo-hexos-5-ulose and D-lyxo-hexos-5-ulose

  所描述的工作涉及从6-脱氧己基-5-烯吡喃糖苷中分离和表征环氧化物以及对其合成潜力的初步探索。延长的环氧化反应时间导致其原位水解，并得到新颖的受保护的D-己糖5糖衍生物（糖1,5-二羰基糖）。研究了己糖5 uloses的一些反应，并在某些情况下分离了七糖苷（七元环糖）衍生物。还描述了在肌醇和氮杂糖的合成和生物合成中作为中间体而感兴趣的D-木糖基己糖5-ulose和D-木糖基己糖5-ulose的新途径。通过NMR和X射线晶体学方法确定了环氧化物和新型5-己糖的结构。
• Action of ultrasound on deoxygenated aqueous solutions of d-glucose
  作者：Helmut Heusinger

  DOI：10.1016/0008-6215(88)84023-0

  日期：1988.10

  Abstract The action of ultrasound on deoxygenated aqueous solutions of d -glucose yielded d -gluconic acid, d - arabino -hexos-2-ulose, d - ribo -hexos-3-ulose, d - xylo -hexos-4- and -5-ulose, d - gluco -hexodialdose, 2-deoxy- d - arabino -hexonic acid, 5-deoxy- d - xylo -hexonic acid, 6-deoxy- l - threo -hexos-4,5-diulose, and 6-deoxy- d - threo -hexos-2,5-diulose. There was little cleavage of the

  摘要超声对d-葡萄糖脱氧水溶液中产生的d-葡萄糖酸，d-阿拉伯糖-hexos-2-ulose，d-ribo-hexos-3-ulose，d-xylo-hexos-4-和-5的作用-ulose，d-葡萄糖-己二醛，2-deoxy- d-arabino-hexonic acid，5-deoxy- d-xylo -hexonic acid，6-deoxy-1-thre -hexos-4,5-diulose和6-脱氧-d-苏-己基-2，5-二糖。碳骨架几乎没有裂开。在超声分析中，脱氧化合物与己糖和己二醛之和的比率小于γ辐照时的比率。
• Process for producing polyhydroxylated piperidines and pyrrolidines and
  申请人：McNeilab, Inc.

  公开号：US05290948A1

  公开（公告）日：1994-03-01

  A process for converting 1,4- and 1,5-dicarbonyl sugars to pyrrolidine and piperidine amino sugars. Novel compounds resulting from this process are also described.

  一种将1,4-和1,5-二羰基糖转化为吡咯烷和哌嗪氨基糖的过程。本发明还描述了由此过程产生的新化合物。