(3AS,5R,6R,6AR)-6-羟基-5-(羟甲基)四氢呋喃并[2,3-D]噁唑-2(5H)-酮 | 2508-81-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 中文名称: (3AS,5R,6R,6AR)-6-羟基-5-(羟甲基)四氢呋喃并[2,3-D]噁唑-2(5H)-酮
• 英文名称: 1-Amino-(1,2-carbamoyl)-α-D-ribofuranose
• 英文别名: 4,5-dihydro-1,2-dideoxy-α-D-ribofuranoso[1,2-d]-1,3-oxazol-2-one；α-D-ribofurano<1,2-d>oxazolidin-2-one；α-D-ribofuro(1',2';4,5)-oxazolidone；(3aS)-6t-hydroxy-5c-hydroxymethyl-(3ar,6ac)-tetrahydro-furo[2,3-d]oxazol-2-one；N,O²-carbonyl-α-D-ribofuranosylamine；D-ribofuranosyl-oxazolidinone；(3aS,5R,6R,6aR)-6-hydroxy-5-(hydroxymethyl)-3a,5,6,6a-tetrahydro-3H-furo[2,3-d][1,3]oxazol-2-one
• CAS: 2508-81-8
• 化学式: C₆H₉NO₅
• 分子量: 175.141
• InChiKey: JHLJBMKXTOOGCW-AIHAYLRMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  88
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (3AS,5R,6R,6AR)-6-羟基-5-(羟甲基)四氢呋喃并[2,3-D]噁唑-2(5H)-酮 在 sodium acetate 作用下， 反应 1.0h， 以76%的产率得到[(3aS,5R,6R,6aR)-3-acetyl-6-acetyloxy-2-oxo-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]oxazol-5-yl]methyl acetate
  参考文献：
  名称：

  与氰酸钾反应将醛糖转变为糖胺1，2-（环状氨基甲酸酯）（糖恶唑烷-2-酮）

  摘要：

  摘要用磷酸氢二钠或氯化铵缓冲水溶液中的氰酸钾水溶液处理戊糖和一些己糖，得到糖胺1,2-（环氨基甲酸酯）{糖呋喃诺（或吡喃）[1,2-d]恶唑烷-2-那些}。大多数产物具有呋喃样结构，但是d-甘露糖和d-lyxose主要产生吡喃糖衍生物。在某些反应中观察到C-2的差向异构。产物及其乙酰化衍生物通过1H-和13C-nmr光谱进行表征。

  DOI：

  10.1016/0008-6215(91)80119-8
• 作为产物：
  描述：

  5-amino-1-[(2,3,5-tri-O-benzoyl-β-D-ribosyl)carbamoyl]-1H-1,2,4-triazole 在 sodium methylate 作用下， 反应 3.0h， 以51%的产率得到(3AS,5R,6R,6AR)-6-羟基-5-(羟甲基)四氢呋喃并[2,3-D]噁唑-2(5H)-酮
  参考文献：
  名称：

  Synthesis of N4-Amino and N4-Hydroxy Derivatives of 5-Azacytidine. A Facile Rearrangement of the N4-Amino Derivative to 5-(3-β-D-Ribofuranosylureido)-1H-1,2,4-triazole

  摘要：

  甲氧基核糖三嗪醇（4）在甲醇中与肼反应生成粗品4-肼基-1-β-D-核糖呋喃糖苷-1,3,5-三嗪-2（1H）-酮（N4-氨基-5-氮杂胞苷）（2），迅速重排为异构体5-核糖尿素三唑（6）。重排在2的水溶液中也很容易进行。碱水解6得到混合物5-尿素三唑（7）和5-氨基三唑（8）。酸水解6只得到7。这种化合物也可通过5-氨基-1-氨基甲酰基三唑（9）的热重排或氰（甲酰）胍氯化水合物与肼反应制备。甲酰化的甲氧基核糖三嗪醇（4a）在甲醇中与肼反应只得到重排产物6a。三苯甲酰核糖异氰酸酯（12）与氨基三唑（8）反应得到1-三唑羧酰胺基三苯甲酰核糖（13），经甲醇解得到噁唑核糖呋喃糖（14）和氨基三唑（8）。化合物14也可通过阻断的核糖氨酸酯（16）的甲醇解获得。甲氧基核糖三嗪醇（4）在甲醇中与羟胺反应生成4-羟胺基-1-β-D-核糖呋喃糖苷-1,3,5-三嗪-2（1H）-酮（N4-羟基-5-氮杂胞苷）（3），在过量羟胺作用下生成1-氰基-1-羟基-5-β-D-核糖呋喃异尿素（19）。甲氧-1,3,5-三嗪醇（18）与甲醇中的羟胺溶液反应生成4-羟胺基-1-甲基-1,3,5-三嗪-2（1H）-酮（N4-羟基-1-甲基-5-氮杂胞嘧啶）（17）。氰（甲酰）胍氯化水合物（10）与羟胺盐酸盐加热反应生成三尿素（21）。讨论了甲氧基核糖三嗪醇（4）与肼和羟胺的反应机制。化合物2、6和19未表现出明显的抗菌或细胞毒活性。

  DOI：

  10.1135/cccc20040905

文献信息

• Selective aqueous acetylation controls the photoanomerization of α-cytidine-5′-phosphate
  作者：Christian Fernández-García、Natalie M. Grefenstette、Matthew W. Powner

  DOI：10.1039/c8cc01929k

  日期：——

  plausible, ribonucleotide α-cytidine-5′-phosphate, selectively protects the vicinal diol moiety. Vicinal diol acetylation blocks oxazolidinone formation and prevents C2′-epimerization upon irradiation with UV-light. Consequently, acetylation enhances (4-fold) the photoanomerization of α-cytidine-5′-phosphate to produce the natural β-pyrimidine ribonucleotide-5′-phosphates required for RNA synthesis.

  核酸是生命系统中信息传递和复制的核心，为达尔文进化提供了分子基础。在这里，我们报告说，非天然的，但益生元似的核糖核苷酸α-胞苷-5'-磷酸的益生元乙酰化选择性保护了邻位二醇部分。邻二醇的乙酰化作用会阻止恶唑烷酮的形成，并在紫外线照射下阻止C2'-表观异构化。因此，乙酰化增强（4-倍）α-胞苷-5'-磷酸的光致异构化，以产生RNA合成所需的天然β-嘧啶核糖核苷酸-5'-磷酸。
• Phosphate-Mediated Interconversion of Ribo- and Arabino-Configured Prebiotic Nucleotide Intermediates
  作者：Matthew W. Powner、John D. Sutherland

  DOI：10.1002/anie.201001662

  日期：2010.6.21

  Flipping stereochemistry: Inorganic phosphate catalyzes the interconversion of ribose and arabinose aminooxazolines, suggesting that the prebiotic synthesis of enantiopure pyrimidine ribonucleotides might have involved a single stereoinversion at C1′ and a double stereoinversion at C2′.

  翻转立体化学：无机磷酸盐催化核糖和阿拉伯糖氨基恶唑啉的相互转化，表明对映纯嘧啶核糖核苷酸的益生元合成可能涉及 C1' 的单个立体反转和 C2' 的双立体反转。
• The decomposition of 1-(.beta.-D-ribofuranosyl)-1,2-dihydropyrimidin-2-one (zebularine) in alkali: mechanism and products
  作者：Joseph J. Barchi、Steven Musser、Victor E. Marquez

  DOI：10.1021/jo00028a026

  日期：1992.1

  The mechanism of the base-catalyzed degradation of 1-(beta-D-ribofuranosyl)-1,2-dihydropyrimidin-2-one (zebularine, 1a) and closely related analogues was studied by NMR spectroscopy and GC-MS. Addition of sodium deuteroxide to a solution of 1a in D2O effected a rapid and irreversible reaction characterized by complete degradation of the heterocyclic pyrimidinone ring. H-1 NMR data suggested that 1a was initially converted to the labile aldehyde 10. This was later confirmed by similar degradation of the 5-fluoro analogue 1b to the more stable aldehyde 9. The alkaline degradation of 1a reaches an end point after 4 h at room temperature with one identifiable product being the anomerized alpha-N1-O2 cyclic carbamate 6. Compound 6 was formed by degradation of both 1a and 1b. The ara epimer 1c formed the beta-carbamate 8, and the 5'-O-methyl derivative 1d proceeded to the 5-O-methyl carbamate 7. An inventory of the remaining atoms yields a formula which suggested the complementary component of the degradation to be an immediate precursor to 1,3-propane dialdehyde (malondialdehyde, MDA). Support for this proposal was evident in both the H-1 and C-13 NMR spectra of the basic reaction mixture which showed resonances that corresponded closely with those published for authentic MDA at pH 9.6. The presence of MDA was unequivocally proven by derivatization of the acidified degradation mixture with hydrazinobenzothiazole (HBT) to give the known adduct 11. GC-MS analysis of the adduct obtained from HBT and the MDA formed during the decomposition reaction was identical to the adduct prepared from authentic MDA and HBT. Since the 5'-O-methyl derivative 1d yielded the same type of products as those analogues with the 5'-hydroxyl free, it was concluded that the 5'-OH was not essential for alkaline lability. This contradicts the original literature assumption that some type of cyclization of the carbohydrate with the pyrimidinone system may be a first step in the mechanism. The data herein suggest that the base-catalyzed decomposition begins with the preferential attack at the 6-position of 2-pyrimidinone nucleosides. The discovery that a known mutagen (MDA) is a product in the degradation of 1a suggests that a relationship could exist between the chemical susceptibility of 1a and its unique biological activity.
• Pithova,P. et al., Collection of Czechoslovak Chemical Communications, 1965, vol. 30, p. 2801 - 2811
  作者：Pithova,P. et al.

  DOI：——

  日期：——
• KOVACS, JOZSEF;PINTER, ISTVAN;LENDERING, URSULA;KOLL, PETER, CARBOHYDR. RES., 210,(1991) C. 155-166
  作者：KOVACS, JOZSEF、PINTER, ISTVAN、LENDERING, URSULA、KOLL, PETER

  DOI：——

  日期：——