D-lyxo-hexos-5-ulose | 80451-84-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: D-lyxo-hexos-5-ulose
• 英文别名: (2S,3R,4S)-2,3,4,6-tetrahydroxy-5-oxohexanal
• CAS: 80451-84-9
• 化学式: C₆H₁₀O₆
• 分子量: 178.142
• InChiKey: ZAVYLQGLQYIKKF-UYFOZJQFSA-N

物化性质

• 熔点：
  158 °C
• 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-lyxo-hexos-5-ulose 在 palladium dihydroxide 氢气 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 、 乙醇 为溶剂， -78.0~25.0 ℃ 、344.73 kPa 条件下， 反应 79.0h， 生成 1-脱氧甘露伊霉素
  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
• 作为产物：
  描述：

  甲基-D-丙噻 在 碳酸氢钠 吡啶 、 咪唑 、 甲醇 、 Oxone 、 1,1,1-三氟丙酮 、 碘 、 edetate disodium 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三苯基膦 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 110.0 ℃ 、13.33 Pa 条件下， 反应 79.5h， 生成 D-lyxo-hexos-5-ulose
  参考文献：
  名称：

  对6-脱氧己基-5-烯吡喃糖苷的环氧化的研究。1,5-二羰基衍生物和D-xylo-hexos-5-ulose和D-lyxo-hexos-5-ulose的新颖合成途径。

  摘要：

  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。

  DOI：

  10.1021/jo016378c

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。
• Novel Synthesis of the Glycosidase Inhibitor Deoxymannojirimycin and of a Synthetic Precursor <scp>d</scp>-<i>l</i><i>yxo</i>-Hexos-5-ulose
  作者：Julie L. O'Brien、Manuela Tosin、Paul V. Murphy

  DOI：10.1021/ol016596s

  日期：2001.10.1

  The synthesis of D-lyxo-hexos-5-ulose (5-ketomannose, 1,5-dicarbonyl sugar), a synthetic precursor to the glycoprocessing inhibitor deoxymannojirimycin, was carried out by an in situ epoxidation and hydrolysis of a trimethylsilyl-protected 6-deoxyhex-5-enopyranoside followed by facile removal of the protecting groups. A novel nine-step synthesis of deoxymannojirimycin has also been achieved from methyl

  [反应：请参见文字]。D-lyxo-hexos-5-ulose（5-酮甘露糖，1，5-二羰基糖）是糖加工抑制剂脱氧甘露糖霉素的合成前体，是通过三甲基甲硅烷基保护的6的原位环氧化和水解进行合成的-deoxyhex-5-enopyranoside，然后轻松除去保护基。还已经从甲基α-D-甘露吡喃糖苷中获得了一种新颖的九步法合成脱氧甘露糖霉素。这涉及从乙酰化的1-azido-6-deoxyhex-5-enopyranoside衍生的环氧化物的甲醇分解，然后脱保护和催化氢化。
• Photochemical oxidation of partially protected derivatives of α-d-glucofuranose and β-d-fructofuranose
  作者：Laetitia Den Drijver、Cedric W. Holzapfel、Martha S. van Dyk、Gert J. Kruger

  DOI：10.1016/0008-6215(87)84006-5

  日期：1987.3

  its 6-pyruvoylation is described. Photolysis of this ester in benzene furnished 5,6- O -isopropylidene-β- d - lyxo -5-ulofuranose, characterised as the O -methyloxime diacetate. Similary, photochemical oxidation of 1 1,2- O -isopropylidene-6- O -pyruvoyl-α- d -glucofuranose gave 1,2- O -isopropylidene-α- d - lgluco -hexodialo1,4:6,3-difuranose in excellent yield.

  摘要描述了一种制备1,2-O-异亚丙基-β-d-果糖呋喃糖及其6-丙酮酸的改进方法。该酯在苯中的光解提供了5,6-O-异亚丙基-β-d-lyxo-5-ulofuranose，特征为O-甲基肟二乙酸酯。类似地，1,2-O-异亚丙基-6-O-丙酮基-α-d-葡萄糖呋喃糖的光化学氧化得到1,2-O-异亚丙基-α-d-l葡萄糖-己二醛1,4：6,3-二呋喃糖。优良的产量。
• 5-Keto-Mannose (D-<i>Lyxo</i>-Hexos-5-Ulose) in Aqueous Solution-Isomeric Composition Dominated by α/β D-Fructofuranose Related Structures
  作者：Donald E. Kiely、Rogers E. Harry-O'Kuru、Philip E. Morris、David W. Morton、James M. Riordan

  DOI：10.1080/07328309708005744

  日期：1997.9

  Selective C-6 hydroxyl triphenylmethylation of methyl 2,3-O-isopropylidene-alpha-D-mannofuranose (1), followed by C-5 hydroxyl oxidation and sequential removal of protecting groups in aqueous acid, yielded D-lyxo-hexos-5-ulose (5-keto-mannose, 5) as a mixture of isomeric forms. The isomeric mixture of 5 in D2O solution was carefully examined using H-1 and C-13 NMR techniques and structural assignments were made for seven isomers. The most prevalent form of 5 observed was the ketofuranose isomer 2S,5R-D-lyxo-hexo-5,2-furanos-5-ulose 1-hydrate (5a, 52 %), with its 2S,5S-ketofuranose anomer (5b) being the next most abundant (14 %). Also identified in the mixture were the alpha and beta-hexofuranos-5-uloses 5c (6 %) and 5d (< 2 %), the pyranose structure 1R,5R-lyxo-hexopyranos-5-ulose 5e (10 %), and the anhydro isomer 1R,5R-1,6-anhydro-D-lyxo-hexopyranos-5-ulose (5f, 5 %), present in a C-1(4) conformation. Limited spectral information suggests that the remaining isomer 5g (8 %) is a hydrated acyclic aldehyde form of 5.
• Kito, Yukio; Kawakishi, Shunro; Namiki, Mitsuo, Agricultural and Biological Chemistry, 1981, vol. 45, # 9, p. 1999 - 2004
  作者：Kito, Yukio、Kawakishi, Shunro、Namiki, Mitsuo

  DOI：——

  日期：——