8-bromo-O3'-(tert-butyldimethylsilyl)-2'-deoxyadenosine | 898253-80-0

• 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: 8-bromo-O3'-(tert-butyldimethylsilyl)-2'-deoxyadenosine
• 英文别名: [(2R,3S,5R)-5-(6-amino-8-bromopurin-9-yl)-3-[tert-butyl(dimethyl)silyl]oxyoxolan-2-yl]methanol
• CAS: 898253-80-0
• 化学式: C₁₆H₂₆BrN₅O₃Si
• 分子量: 444.404
• InChiKey: HRGHXKWRHNPNIN-HBNTYKKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.84
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  108
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  8-bromo-O3'-(tert-butyldimethylsilyl)-2'-deoxyadenosine 在 air 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 作用下， 以 乙腈 为溶剂， 反应 2.0h， 以38%的产率得到(5'S)-O₃'-(tert-butyldimethylsilyl)-5',8-cyclo-2'-deoxyadenosine
  参考文献：
  名称：

  C5‘-Adenosinyl Radical Cyclization. A Stereochemical Investigation

  摘要：

  A variety of substituted 2'-deoxyadenosin-5'-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5'S,8R)-4 and (5'R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5'-radical cyclization have been considered. The observed increase of the (5'S)/(5'R) ratio by increasing the bulkiness of the R-1 group is explained in terms of steric repulsion between R-1 and the purine moiety which favors the C5'-endo conformation, whereas the effect of the water solvent in promoting the (5'R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5'-exo confomation.

  DOI：

  10.1021/jo060197z
• 作为产物：
  描述：

  8-溴-2'-脱氧腺苷 在 咪唑 、 4-二甲氨基吡啶 、 水 、 三氟乙酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 8-bromo-O3'-(tert-butyldimethylsilyl)-2'-deoxyadenosine
  参考文献：
  名称：

  C5‘-Adenosinyl Radical Cyclization. A Stereochemical Investigation

  摘要：

  A variety of substituted 2'-deoxyadenosin-5'-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5'S,8R)-4 and (5'R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5'-radical cyclization have been considered. The observed increase of the (5'S)/(5'R) ratio by increasing the bulkiness of the R-1 group is explained in terms of steric repulsion between R-1 and the purine moiety which favors the C5'-endo conformation, whereas the effect of the water solvent in promoting the (5'R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5'-exo confomation.

  DOI：

  10.1021/jo060197z

文献信息

• C5‘-Adenosinyl Radical Cyclization. A Stereochemical Investigation
  作者：Maria Luisa Navacchia、Chryssostomos Chatgilialoglu、Pier Carlo Montevecchi

  DOI：10.1021/jo060197z

  日期：2006.6.1

  A variety of substituted 2'-deoxyadenosin-5'-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5'S,8R)-4 and (5'R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5'-radical cyclization have been considered. The observed increase of the (5'S)/(5'R) ratio by increasing the bulkiness of the R-1 group is explained in terms of steric repulsion between R-1 and the purine moiety which favors the C5'-endo conformation, whereas the effect of the water solvent in promoting the (5'R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5'-exo confomation.