5-Acetoxy-1-(benzyloxy)methyl-3-(methoxymethyl)pyrrolo<2,3-d>pyrimidine-2,4-dione | 159626-05-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯并嘧啶类
• 英文名称: 5-Acetoxy-1-(benzyloxy)methyl-3-(methoxymethyl)pyrrolo<2,3-d>pyrimidine-2,4-dione
• 英文别名: [3-(methoxymethyl)-2,4-dioxo-1-(phenylmethoxymethyl)-7H-pyrrolo[2,3-d]pyrimidin-5-yl] acetate
• CAS: 159626-05-8
• 化学式: C₁₈H₁₉N₃O₆
• 分子量: 373.365
• InChiKey: QWIWNJMUDLRAQZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  27
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-Α-氯-3,5-二-O-对甲苯甲酰基-2-脱氧-D-呋喃核糖 、 5-Acetoxy-1-(benzyloxy)methyl-3-(methoxymethyl)pyrrolo<2,3-d>pyrimidine-2,4-dione 在 sodium hydride 作用下， 以 乙腈 为溶剂， 生成 5-Acetoxy-1-<(benzyloxy)methyl>-7-<2'-deoxy-3',5'-di-O-(p-toluoyl)-β-D-erythro-pentofuranosyl>-3-(methoxymethyl)pyrrolo<2,3-d>pyrimidine-2,4-dione 、 5-Acetoxy-1-<(benzyloxy)methyl>-7-<2'-deoxy-3',5'-di-O-(p-toluoyl)-α-D-erythro-pentofuranosyl>-3-(methoxymethyl)pyrrolo<2,3-d>pyrimidine-2,4-dione
  参考文献：
  名称：

  A New Synthetic Route to .beta.-2'-Deoxyribosyl-5-Substituted Pyrrolo[2,3-d]pyrimidines. Synthesis of 2'-Deoxycadeguomycin

  摘要：

  A new and flexible synthetic route to beta-2'-deoxyribosyl-5-substituted pyrrolo[2,3-d]pyrimidines has been developed. Formation of the pyrrole ring is effected by combining sodium N-(4-nitrophenethyl)-glycinate with a differently protected 6-chlorouracil derivative generating a substitution adduct. Heating of his material in acetic anhydride affords the 5-(acetyloxy)pyrrolo[2,3-d]pyrimidine 9 in high yield. Base-mediated removal of the pyrrole protecting group gives free pyrrole 10 which is then glycosylated with 1-chloro-2-deoxy-3,5-ditoluoyl-alpha-D-erythro-pentofuranose (11) using the sodium salt method. The resulting glycosides 15a,b (alpha:beta, 1:4) are readily separated following hydrolysis of the C-5 acetyloxy group. The subsequently derived pure beta-5-(trifluoromethanesulfonyl) derivative 14 undergoes four types of palladium-catalyzed carbon-carbon bond-forming reactions and results in C-5 substituted compounds 15-18. An efficient synthetic route to the pyrrolo[2,3-d]pyrimidine nucleotide analogue, 2'-deoxycadeguomycin (27), is presented. The key transformation involves the conversion of the differentially protected pyrrolo[2,3-d]pyrimidine-2,4-dione base portion in 15 into a protected 2-aminopyrrolo[2,3-d]pyrimidin-4-one 24. An alternative route to 27 was developed which involved prior conversion of the pyrrole-protected precursor 9 into its C-5 triflate derivative 20 followed by palladium-catalyzed carboxylation leading to ester 21. Removal of the pyrrole protecting group and then sodium salt-promoted glycosidation afforded the same beta-2'-deoxyribosyl intermediate 15 as prepared earlier. The stereochemistry of glycosidation was found to be dependent upon the electronic effect of the C-5 substituent on the pyrrole ring.

  DOI：

  10.1021/jo00121a027
• 作为产物：
  描述：

  1-<(Benzyloxy)methyl>-6-chlorouracil 在 三正丙胺 、 sodium hydroxide 、 lithium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 0.25h， 生成 5-Acetoxy-1-(benzyloxy)methyl-3-(methoxymethyl)pyrrolo<2,3-d>pyrimidine-2,4-dione
  参考文献：
  名称：

  A New Efficient Route to 5-Substituted .beta.-2'-Deoxyribosylpyrrolo[2,3-d]pyrimidines. Palladium-Catalyzed Functionalizations of a C-5 Triflate Intermediate

  摘要：

  An efficient synthesis of a beta-2'-deoxyribosyl-5 -[(trifluoromethanesulfonyl)oxy]pyrrolo[2,3-d]pyrimidine- 2,4-dione 9, starting from 6-chlorouracil, is presented along with its subsequent functionalization at C-5 using four types of palladium-catalyzed reactions.

  DOI：

  10.1021/jo00102a011