5-(1-fluoro-2-propenyl)-1-(5-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole-4-carboxamide | 247024-30-2

• 英文名称: 5-(1-fluoro-2-propenyl)-1-(5-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole-4-carboxamide
• CAS: 247024-30-2
• 化学式: C₂₁H₃₄FN₃O₅Si
• 分子量: 455.602
• InChiKey: TUDRBPGOJAYUGE-LRJLTRIWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  31.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  97.83
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  5-(1-fluoro-2-propenyl)-1-(5-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole-4-carboxamide 在 4-二甲氨基吡啶 、 potassium permanganate 、 18-冠醚-6 、 sodium carbonate 作用下， 以 四氢呋喃 、 吡啶 、 乙醇 、 氯仿 、 水 为溶剂， 反应 20.5h， 生成 7-fluoro-1-(5-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-D-ribofuranosyl)imidazo[4,5-c]pyridin-4(5H)-one
  参考文献：
  名称：

  Nucleosides and Nucleotides. 184. Synthesis and Conformational Investigation of Anti-Fixed 3-Deaza-3-halopurine Ribonucleosides^1,2

  摘要：

  A versatile synthetic route to 3-deaza-3-haloinosines 6-8 and 46, -adenosines 15-17 and 64, and -guanosines 25, 26, and 52 is described. 3-Deaza-3-chloro-, -bromo-, and -iodopurine ribonucleosides can be synthesized by treating the 3-deazapurine ribonucleosides with N-halosuccinimides. For the synthesis of 3-deaza-3-fluoropurine ribonucleosides, 5-formylimidazole-4-carboxamide ribosides 34 and 35 prepared from 5-iodoimidazole-4-carboxamide derivatives 29 and 31 were us ed as the key intermediates. The reaction of 34 and 35 with lithium (trimethylsilyl)acetylide and sodium cyanide, respectively, followed by appropriate manipulations gave 3-deaza-3-fluoroinosine derivative 46 and 3-deaza-3-fluoroguanosine derivative 52. 3-Deaza-3-fluoroadenosine (64) was also synthesized by selective reductive deamination of 4,6-diamino-7-fluoroimidazo[4,5-c]pyridine derivative 51, followed by deprotection. A conformational analysis using H-1 NMR and NOE experiments showed that the introduction of halogens (chloro, bromo, and iodo) into the 3-position of 3-deazapurine ribonucleosides forced fixation of the glycosyl torsion angle in the anti region, but did not-abnormally influence sugar puckering. On the other hand, 3-deaza-3-fluoropurine ribonucleosides should rotate freely around the glycosyl bond.

  DOI：

  10.1021/jo990638x
• 作为产物：
  描述：

  5-(1-hydroxypropynyl)-1-(5-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole-4-carboxamide 在 Lindlar's catalyst 二乙胺基三氟化硫 、 氢气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， -15.0~20.0 ℃ 、344.74 kPa 条件下， 反应 16.0h， 生成 5-(1-fluoro-2-propenyl)-1-(5-O-tert-butyldimethylsilyl-2,3-O-isopropylidene-β-D-ribofuranosyl)imidazole-4-carboxamide
  参考文献：
  名称：

  Nucleosides and Nucleotides. 184. Synthesis and Conformational Investigation of Anti-Fixed 3-Deaza-3-halopurine Ribonucleosides^1,2

  摘要：

  A versatile synthetic route to 3-deaza-3-haloinosines 6-8 and 46, -adenosines 15-17 and 64, and -guanosines 25, 26, and 52 is described. 3-Deaza-3-chloro-, -bromo-, and -iodopurine ribonucleosides can be synthesized by treating the 3-deazapurine ribonucleosides with N-halosuccinimides. For the synthesis of 3-deaza-3-fluoropurine ribonucleosides, 5-formylimidazole-4-carboxamide ribosides 34 and 35 prepared from 5-iodoimidazole-4-carboxamide derivatives 29 and 31 were us ed as the key intermediates. The reaction of 34 and 35 with lithium (trimethylsilyl)acetylide and sodium cyanide, respectively, followed by appropriate manipulations gave 3-deaza-3-fluoroinosine derivative 46 and 3-deaza-3-fluoroguanosine derivative 52. 3-Deaza-3-fluoroadenosine (64) was also synthesized by selective reductive deamination of 4,6-diamino-7-fluoroimidazo[4,5-c]pyridine derivative 51, followed by deprotection. A conformational analysis using H-1 NMR and NOE experiments showed that the introduction of halogens (chloro, bromo, and iodo) into the 3-position of 3-deazapurine ribonucleosides forced fixation of the glycosyl torsion angle in the anti region, but did not-abnormally influence sugar puckering. On the other hand, 3-deaza-3-fluoropurine ribonucleosides should rotate freely around the glycosyl bond.

  DOI：

  10.1021/jo990638x

文献信息

• Nucleosides and Nucleotides. 138. Synthesis of 3-Halo-3-deazainosines: Conformational Lock with the Halogen at the 3-Position of the 3-Deazainosine in anti-Conformation
  作者：Noriaki Minakawa、Naoshi Kojima、Akira Matsuda

  DOI：10.3987/com-95-s57

  日期：——

  Synthesis of 3-chloro-, bromo-, and iodo-3-deazainosines (6-8) can be done by treatment of the 3-deazainosine derivative (2) with N-halosuccinimides. Treatment of the 5-formylimidazole derivative (11) with vinylmagnesium bromide gave 5-(1-hydroxy-2-propenyl)imidazole derivative (12), followed by fluorination and appropriate manipulations to cyclize, affording 3-fluoro-3-deazainosine (18). Although free rotation around the glycosyl linkage in 3-deazainosine (1) and 18 was observed, those of 6, 7, and 8 were rather fixed in the anti-conformation as analyzed by nOe experiments.