-2',3',5'-tris-O-(methoxymethyl)uridine-6-caboxaldehyde | 138386-00-2

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: -2',3',5'-tris-O-(methoxymethyl)uridine-6-caboxaldehyde
• 英文别名: 2',3',5'-tris-O-(methoxymethyl)uridine-6-carboxaldehyde-formyl-13C；3-[(2R,3R,4R,5R)-3,4-bis(methoxymethoxy)-5-(methoxymethoxymethyl)oxolan-2-yl]-2,6-dioxopyrimidine-4-carbaldehyde
• CAS: 138386-00-2
• 化学式: C₁₆H₂₄N₂O₁₀
• 分子量: 405.363
• InChiKey: QGHSYJHJUXMFSZ-BANURSLUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.15
• 重原子数：
  28.0
• 可旋转键数：
  12.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  136.54
• 氢给体数：
  1.0
• 氢受体数：
  11.0

反应信息

• 作为反应物：
  描述：

  -2',3',5'-tris-O-(methoxymethyl)uridine-6-caboxaldehyde 在 水 作用下， 以 氘代二甲亚砜 为溶剂， 生成 6-(dihydroxymethyl)-2',3',5'-tris-O-(methoxymethyl)uridine-hydrate-13C
  参考文献：
  名称：

  Facile addition of hydroxylic nucleophiles to the formyl group of uridine-6-carboxaldehydes

  摘要：

  The ''instability'' previously ascribed to the tri-O-protected 6-formyluridines has been shown to be due to a facile hydration of the aldehyde functionality. Using an efficient protecting group strategy, 2',3',5'-tris-O-(methoxymethyl)uridine-6-carboxaldehyde (2) was prepared in two steps from uridine. Aldehyde 2 was shown to undergo a reversible hydration reaction in (CD3)2SO solution to give the gem-diol 3, according to extensive H-1 and C-13 1D and 2D NMR spectroscopic analyses. This gem-diol was the sole structure detected in D2O solution. The diethyl acetal derivative 4 provided spectral data for comparison to that of 3. Compound 2 afforded diastereomeric hemiacetal products upon treatment with alcohols, and deprotection of 2 afforded the heretofore unknown uridine-6-carboxaldehyde, which was found to exist as a 1:10 mixture of free aldehyde A and a 5'-cyclic hemiacetal structure D in dry (CD3)2SO solution, but as a 1:2 mixture of a 5'-cyclic hemiacetal structure D and the gem-diol B in D2O solution, by NMR.

  DOI：

  10.1021/jo00029a027
• 作为产物：
  描述：

  尿嘧啶核苷 在 三氟甲磺酸 lithium diisopropyl amide 作用下， 以 二氯甲烷 为溶剂， 反应 7.0h， 生成 -2',3',5'-tris-O-(methoxymethyl)uridine-6-caboxaldehyde
  参考文献：
  名称：

  Facile addition of hydroxylic nucleophiles to the formyl group of uridine-6-carboxaldehydes

  摘要：

  The ''instability'' previously ascribed to the tri-O-protected 6-formyluridines has been shown to be due to a facile hydration of the aldehyde functionality. Using an efficient protecting group strategy, 2',3',5'-tris-O-(methoxymethyl)uridine-6-carboxaldehyde (2) was prepared in two steps from uridine. Aldehyde 2 was shown to undergo a reversible hydration reaction in (CD3)2SO solution to give the gem-diol 3, according to extensive H-1 and C-13 1D and 2D NMR spectroscopic analyses. This gem-diol was the sole structure detected in D2O solution. The diethyl acetal derivative 4 provided spectral data for comparison to that of 3. Compound 2 afforded diastereomeric hemiacetal products upon treatment with alcohols, and deprotection of 2 afforded the heretofore unknown uridine-6-carboxaldehyde, which was found to exist as a 1:10 mixture of free aldehyde A and a 5'-cyclic hemiacetal structure D in dry (CD3)2SO solution, but as a 1:2 mixture of a 5'-cyclic hemiacetal structure D and the gem-diol B in D2O solution, by NMR.

  DOI：

  10.1021/jo00029a027

文献信息

• A new class of nucleosides possessing unusual physical properties: syntheses, hydration, and structural equilibria of 1-(.beta.-D-glycofuranosyl)uracil-6-carboxaldehydes
  作者：Michael P. Groziak、Ali Koohang、William C. Stevens、Paul D. Robinson

  DOI：10.1021/jo00067a044

  日期：1993.7

  The 1-beta-D-ribofruanosyl, 1-(2'-deoxy-beta-D-ribofuranosyl), and 1-beta-D-arabinofuranosyl derivatives (1a-c) of uracil-6-carboxaldehyde have been prepared for physicochemical analysis. The NMR-determined hydration and structural equilibria of 1a-c in both D2O and (CD3)2SO solution are compared, and the single-crystal X-ray structure of 1a is presented. Due to the high degree of electrophilic nature of their aldehyde moiety, all three nucleosides exhibit a strong ProclivitY toward existing as cyclic hemiacetal structures in solution; one such structure was found to be the sole constituent in the solid state for 1a. Using a [formyl-C-13]-labeled derivative of a synthetic precursor to 1a, the 1DELTAC-13(O-18) shielding isotope shift effects produced upon hydrate formation were determined at a +/- 1 ppb level, giving reference values of biomechanistic importance.