9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-6-(imidazol-1-yl)purine | 385806-21-3

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: 9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-6-(imidazol-1-yl)purine
• 英文别名: 2',3',5'-tri-O-acetyl-6-(imidazol-1-yl)nebularine；[(2R,3R,4R,5R)-3,4-diacetyloxy-5-(6-imidazol-1-ylpurin-9-yl)oxolan-2-yl]methyl acetate
• CAS: 385806-21-3
• 化学式: C₁₉H₂₀N₆O₇
• 分子量: 444.404
• InChiKey: TUIXSGMONZCGOR-NVQRDWNXSA-N

物化性质

• 沸点：
  647.7±65.0 °C(Predicted)
• 密度：
  1.58±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  32
• 可旋转键数：
  9
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  150
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-6-(imidazol-1-yl)purine 在 氨 作用下， 以 甲醇 为溶剂， 反应 26.0h， 生成 6-苄基腺苷
  参考文献：
  名称：

  嘌呤2'-脱氧核苷和核糖核苷在C6的轻度和高效功能化。

  摘要：

  [反应：请参见文本]用环状仲胺或咪唑和I（2）/ Ph（3）P / EtN（i-Pr）（2）/（CH（ 2）Cl（2）或甲苯）定量转化为6-N-（取代）嘌呤核苷。与6-（咪唑-1-基）衍生物的S（N）Ar反应得到6-（N，O或S）-取代的产物。在环境温度下用芳基胺对6-（苄基磺酰基）进行S（N）Ar取代。

  DOI：

  10.1021/ol000255h
• 作为产物：
  描述：

  咪唑 、 2’,3’,5’-三乙酰肌苷 在 碘 、 N,N-二异丙基乙胺 、 三苯基膦 作用下， 以 甲苯 为溶剂， 反应 0.83h， 生成 9-(2,3,5-tri-O-acetyl-β-D-ribofuranosyl)-6-(imidazol-1-yl)purine
  参考文献：
  名称：

  嘌呤2'-脱氧核苷和核糖核苷在C6的轻度和高效功能化。

  摘要：

  [反应：请参见文本]用环状仲胺或咪唑和I（2）/ Ph（3）P / EtN（i-Pr）（2）/（CH（ 2）Cl（2）或甲苯）定量转化为6-N-（取代）嘌呤核苷。与6-（咪唑-1-基）衍生物的S（N）Ar反应得到6-（N，O或S）-取代的产物。在环境温度下用芳基胺对6-（苄基磺酰基）进行S（N）Ar取代。

  DOI：

  10.1021/ol000255h

文献信息

• 6-Bromopurine Nucleosides as Reagents for Nucleoside Analogue Synthesis
  作者：Eduardo A. Véliz、Peter A. Beal

  DOI：10.1021/jo016078v

  日期：2001.12.1

  Surprisingly facile direct substitution reactions with acetyl-protected 6-bromopurine nucleosides are described. Included in the series of bromonucleosides studied is the guanosine derivative N(2)-2',3',5'-tetraacetyl-6-bromopurine ribonucleoside, the synthesis of which is reported here for the first time. Brominated nucleosides had not previously been considered optimal substrates for S(N)Ar reactions given

  令人惊讶地描述了用乙酰基保护的6-溴嘌呤核苷的容易的直接取代反应。所研究的溴代核苷系列中包括鸟苷衍生物N（2）-2'，3'，5'-四乙酰基-6-溴嘌呤核糖核苷，此处首次报道了其合成。鉴于卤代芳族体系的总体反应趋势（即F> Cl> Br> I），溴化核苷以前未被认为是S（N）Ar反应的最佳底物。然而，即使是弱亲核的芳族胺，在极性溶剂中也具有这些6-溴嘌呤核苷的高产率取代产物。对于伯芳族胺，脂族仲胺和咪唑，反应仅在C6发生，而对乙酰基保护的核糖没有影响。此外，我们报道了3'，5'-二-O-乙酰基-6-溴嘌呤-2'-脱氧核糖核苷的首次合成及其在不添加金属催化剂的情况下与MeOH中的芳基胺反应。因此，腺苷和2'-脱氧腺苷的C6-芳基胺衍生物可以通过与相应的6-溴前体进行简单的S（N）Ar反应来制备。我们还描述了在添加碱（DBU）存在下使用乙醇和硫醇亲核试剂与6-溴核苷的高产率和C6选择性取代反应。
• Synthesis of N6,N6-Dialkyladenine Nucleosides Using Hexaalkylphosphorus Triamides Produced in Situ
  作者：Mahesh K. Lakshman、Asad Choudhury、Suyeal Bae、Eliezer Rochttis、Padmanava Pradhan、Amit Kumar

  DOI：10.1002/ejoc.200800752

  日期：——

  Reactions between secondary amines and phosphorus trichloride (PCl3) leads to the formation of the corresponding tris(dialkylamino)phosphines or hexaalkylphosphorus triamides [HAPT: (R2N)3P]. Reaction of silyl-protected 2'-deoxyinosine and acetyl-protected inosine with the in situ formed HAPT and iodine (I2) leads to the formation of N6,N6-dialkyl adenosine and 2'-deoxyadenosine. In some cases the

  仲胺与三氯化磷 (PCl3) 之间的反应导致形成相应的三（二烷基氨基）膦或六烷基磷三酰胺 [HAPT: (R2N)3P]。甲硅烷基保护的 2'-脱氧肌苷和乙酰基保护的肌苷与原位形成的 HAPT 和碘 (I2) 的反应导致形成 N6,N6-二烷基腺苷和 2'-脱氧腺苷。在某些情况下，胺的化学计量与叔胺碱的使用一样重要。通过 31 P1H} NMR 研究了胺化学计量对 HAPT 与 I2 反应的影响。
• Structure and Synthesis of 6-(Substituted-imidazol-1-yl)purines:  Versatile Substrates for Regiospecific Alkylation and Glycosylation at N9¹
  作者：Minghong Zhong、Ireneusz Nowak、John F. Cannon、Morris J. Robins

  DOI：10.1021/jo060340o

  日期：2006.5.1

  X-ray crystal structures of several 6-(azolyl) purine base and nucleoside derivatives show essentially coplanar conformations of the purine and appended 6-(azolyl) rings. However, the planes of the purine and imidazole rings are twisted similar to 57 degrees in a 2-chloro-6-(4,5-diphenylimidazol-1-yl) purine nucleoside, and a twist angle of similar to 61 degrees was measured between the planes of the purine and pyrrole rings in the structure of a 6-(2,5-dimethylpyrrol-1-yl) purine nucleoside derivative. Shielding "above" N7 of the purine ring by a proximal C-H on the 6-azolyl moiety is apparent with the coplanar compounds, but this effect is diminished in those without coplanarity. Syntheses of 6-(azolyl)purines from both base and nucleoside starting materials are described. Treatment of 2,6- dichloropurine with imidazole gave 2-chloro-6-(imidazol)-yl)purine. Modified Appel reactions at C6 of trityl-protected hypoxanthine and guanine derivatives followed by detritylation gave 6-(imidazol-1-yl)- and 2-amino-6-(imidazol-1-yl) purines. Imidazole was introduced at C6 of 2',3',5'-tri-O-acetylinosine by a modified Appel reaction, and solvolysis of the glycosyl linkage gave 6-(imidazol-1-yl) purine. Guanosine triacetate was transformed into the protected 2,6-dichloropurine nucleoside, which was subjected to SNAr displacement with imidazoles at C6 followed by glycosyl solvolysis to provide 2-chloro-6-(substituted-imidazol-1-yl) purines. Potential applications of these purine derivatives are outlined.
• Selective Removal of the 2‘- and 3‘-<i>O</i>-Acyl Groups from 2‘,3‘,5‘-Tri-<i>O</i>-acylribonucleoside Derivatives with Lithium Trifluoroethoxide¹
  作者：Ireneusz Nowak、Carl T. Jones、Morris J. Robins

  DOI：10.1021/jo0600104

  日期：2006.4.1

  Selective cleavage of O2' and O3' ester groups from ribonucleoside derivatives has been accomplished with Dowex 1 x 2 (CF3CH2O-) in 2,2,2-trifluoroethanol (TFE) or lithium trifluoroethoxide/TFE. Deacylations with Li+ -OCH2CF3/TFE proceed at ambient temperature (or with mild heating) to give the 5'-O-acyl derivatives in superior yields and higher purity than prior approaches for selective O2' and O3' ester deprotection.