(+/-)-1-<2a,5-Didehydro-2a-carba-β-psicofuranosyl>uracil

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 核苷和核苷酸类似物
• 英文名称: (+/-)-1-<2a,5-Didehydro-2a-carba-β-psicofuranosyl>uracil
• 英文别名: 1-[(1S,4R,5S)-4,5-dihydroxy-1,3-bis(hydroxymethyl)cyclopent-2-en-1-yl]pyrimidine-2,4-dione
• 化学式: C₁₁H₁₄N₂O₆
• 分子量: 270.242
• InChiKey: QCRJKGMDJACIFO-KKZNHRDASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.9
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  130
• 氢给体数：
  5
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  (+/-)-6-O-Benzyl-3,4-O-isopropylidene-1,2-anhydro-2a,5-didehydro-2a-carba-α-psicofuranose 在 Lindlar's catalyst ammonium hydroxide 、 tetrafluoroboric acid 、 硫酸 、 三氟化硼乙醚 、 氢气 、 三溴化硼 、 sodium hydride 、 三氟乙酸 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 、 苯 为溶剂， 反应 55.55h， 生成 (+/-)-1-<2a,5-Didehydro-2a-carba-β-psicofuranosyl>uracil
  参考文献：
  名称：

  Synthesis of carbocyclic analogs of 1-.beta.-D-psicofuranosyl nucleosides. psico-Cyclopentenyladenosine (psicoplanocin A) and psico-cyclopentenylcytosine

  摘要：

  Psicoplanocin A (4a) and psico-cyclopentenylcytosine (4b) represent the first two known examples of carbocyclic ketohexose nucleosides. These two stable compounds combine structural features of two known classes of natural products: neplanocin A and the ketohexose nucleosides psicofuranine (1a) and decoynine (2). Both compounds were synthesized in racemic form from (+/-)-cyclopentenone 5, which in turn was available froM D-ribonolactone. Construction of the surrogate glycon moiety commenced with the attachment of a protected hydroxymethyl fragment onto the ketone carbonyl of 5 via nucleophilic addition of [(benzoyloxy)methyl]lithium to give intermediate 7. Introduction of the requisite nitrogen at the tertiary allylic carbon of 7 was achieved by the BF3.OEt2-catalyzed addition of hydrazoic acid to a generated transitional allylic cation. This method produced the epimeric azides 8a and 8b, and following conversion of the beta-azide (8a) to the corresponding carbocyclic amine, the purine and pyrimidine rings of psicoplanocin A and psico-cyclopentenylcytosine were constructed by conventional methods. An X-ray crystallographic analysis corroborated the structure of psicoplanocin A determined from NOE experiments on the epimeric azides. Both psicoplanocin A and psico-cyclopentenylcytosine were found to be devoid of cell cytotoxicity and in vitro antiviral activity.

  DOI：

  10.1021/jo00074a030

文献信息

• Synthesis of carbocyclic analogs of 1-.beta.-D-psicofuranosyl nucleosides. psico-Cyclopentenyladenosine (psicoplanocin A) and psico-cyclopentenylcytosine
  作者：Michael Bodenteich、Victor E. Marquez、Joseph J. Barchi、Wendy H. Hallows、Barry M. Goldstein、John S. Driscoll

  DOI：10.1021/jo00074a030

  日期：1993.10

  Psicoplanocin A (4a) and psico-cyclopentenylcytosine (4b) represent the first two known examples of carbocyclic ketohexose nucleosides. These two stable compounds combine structural features of two known classes of natural products: neplanocin A and the ketohexose nucleosides psicofuranine (1a) and decoynine (2). Both compounds were synthesized in racemic form from (+/-)-cyclopentenone 5, which in turn was available froM D-ribonolactone. Construction of the surrogate glycon moiety commenced with the attachment of a protected hydroxymethyl fragment onto the ketone carbonyl of 5 via nucleophilic addition of [(benzoyloxy)methyl]lithium to give intermediate 7. Introduction of the requisite nitrogen at the tertiary allylic carbon of 7 was achieved by the BF3.OEt2-catalyzed addition of hydrazoic acid to a generated transitional allylic cation. This method produced the epimeric azides 8a and 8b, and following conversion of the beta-azide (8a) to the corresponding carbocyclic amine, the purine and pyrimidine rings of psicoplanocin A and psico-cyclopentenylcytosine were constructed by conventional methods. An X-ray crystallographic analysis corroborated the structure of psicoplanocin A determined from NOE experiments on the epimeric azides. Both psicoplanocin A and psico-cyclopentenylcytosine were found to be devoid of cell cytotoxicity and in vitro antiviral activity.