L-arabino-hexos-5-ulose | 134039-12-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: L-arabino-hexos-5-ulose
• 英文别名: 5-oxo-D-galactose；(2R,3R,4R)-2,3,4,6-tetrahydroxy-5-oxohexanal
• CAS: 134039-12-6
• 化学式: C₆H₁₀O₆
• 分子量: 178.142
• InChiKey: ZAVYLQGLQYIKKF-LFRDXLMFSA-N

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：

  L-arabino-hexos-5-ulose 在 吡啶 、 sodium cyanoborohydride 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 74.0h， 生成 2,3,4,6-tetra-O-acetyl-N-benzhydryl-1,5-dideoxy-1,5-imino-D-galactitol
  参考文献：
  名称：

  Double reductive amination of l-arabino-hexos-5-uloses: A diastereoselective approach to 1-deoxy-d-galactostatin derivatives

  摘要：

  The double reductive amination of L-arabino-hexos-5-ulose with benzhydrylamine and NaBH3CN takes place in a diastereospecific manner giving in moderate chemical yield (36%) the galactosidase inhibitor 1-deoxy-D-galactostatin. The aminocyclization of 2,6-di-O-benzyl-L-arabino-hexos-5-ulose is more complicated giving results dependent from the type of amine: with ammonia or methylamine a mixture of C-5 epimeric 1-deoxyazapyranoses (D-galacto/L-altro ratio approximate to 4:1) is obtained in 45-65% combined yield, while with benzhydrylamine substantial amounts of an acyclic 1-deoxyl-benzydrylamino-hexitol (10% yield) is isolated together with the expected 1-deoxy-azasugars of the D-galacto and L-altro series. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00063-x
• 作为产物：
  描述：

  uridine 5'-diphosphate-5-fluoro-α-D-galactopyranose 在 sodium dithionite 、 uridine 5'-diphosphate-galactopyranose mutase 作用下， 反应 3.0h， 生成 L-arabino-hexos-5-ulose
  参考文献：
  名称：

  Study of Uridine 5′-Diphosphate (UDP)-Galactopyranose Mutase Using UDP-5-Fluorogalactopyranose as a Probe: Incubation Results and Mechanistic Implications

  摘要：

  Uridine 5'-diphosphate-5-fluorogalactopyranose (UDP-SF-Galp, 7) was synthesized, and its effect on UDP-Galp mutase (UGM) was investigated. UGM facilitated the hydrolysis of 7 to yield UDP and 5-oxogalactose (24), but no 11 was detected. F-19 NMR and trapping experiments demonstrated that the reaction involves the initial formation of a substrate-cofactor adduct followed by decomposition of the resulting C5 gem-fluorohydrin to generate a 5-oxo intermediate (10). The results support the current mechanistic proposal for UGM and suggest new directions for designing mechanism-based inhibitors.

  DOI：

  10.1021/acs.orglett.6b01618

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。
• A simple stereospecific route to 5-C-alkoxy-D-galactopyransides and to L-arabino-hexos-5-uloses
  作者：Pier Luigi Barili、Giancarlo Berti、Giorgio Catelani、Felicia D'Andrea

  DOI：10.1016/s0040-4039(00)92130-0

  日期：1991.2

  5-C-alkoxy-β-D-galactopyranosides, which are easily convertible into L-arabino-hexos-5-uloses, can be prepared from β-D-galactopyranosides via peroxyacid oxidation in an alcoholic solvent of intermediate 4-deoxy-α-L-threo-hex-4-enopyranosides.

  可以容易地转化为L-阿拉伯糖-己糖-5-uloses的5-C-烷氧基-β-D-吡喃半乳糖苷可以由β-D-吡喃半乳糖苷在中间体4-脱氧-α的醇溶剂中通过过氧酸氧化制备-L-苏式-hex-4-enopyranosides。
• [EN] SYNTHESIS OF AN AZASUGAR AND INTERMEDIATES THEREOF<br/>[FR] SYNTHÈSE D'UN AZASUCRE ET DE SES INTERMÉDIAIRES
  申请人：DIPHARMA FRANCIS SRL

  公开号：WO2019020362A1

  公开（公告）日：2019-01-31

  The present invention relates to a process for the preparation of migalastat of formula (I) and intermediates useful in the synthesis thereof. The process comprises the double reductive amination reaction of a compound of formula (VI).

  本发明涉及一种制备式(I)米加拉斯塔的方法及其合成中间体。该方法包括式(VI)化合物的双还原胺化反应。
• Synthesis of an azasugar and intermediates thereof
  申请人：DIPHARMA SA

  公开号：US11180454B2

  公开（公告）日：2021-11-23

  The present invention relates to a process for the preparation of migalastat of formula (I) and intermediates useful in the synthesis thereof. The process comprises the double reductive amination reaction of a compound of formula (VI).

  本发明涉及一种制备式（I）米加司他及其合成中间体的工艺。该工艺包括式（VI）化合物的双还原胺化反应。
• Barili, Pier Luigi; Berti, Giancarlo; Catelani, Giorgio, Gazzetta Chimica Italiana, 1992, vol. 122, # 4, p. 135 - 142
  作者：Barili, Pier Luigi、Berti, Giancarlo、Catelani, Giorgio、D'Andrea, Felicia

  DOI：——

  日期：——