(5'S,8R)-N-benzoyl-O3'-(tert-butyldimethylsilyl)-5',8-cyclo-7,8-dihydro-2'-deoxyadenosine | 898253-81-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: (5'S,8R)-N-benzoyl-O3'-(tert-butyldimethylsilyl)-5',8-cyclo-7,8-dihydro-2'-deoxyadenosine
• 英文别名: N-[(1R,10R,11S,12R,13S)-13-[tert-butyl(dimethyl)silyl]oxy-11-hydroxy-15-oxa-2,4,6,9-tetrazatetracyclo[10.2.1.02,10.03,8]pentadeca-3,5,7-trien-7-yl]benzamide
• CAS: 898253-81-1
• 化学式: C₂₃H₃₁N₅O₄Si
• 分子量: 469.616
• InChiKey: UOEPGEJGDVZDTK-BSEUJLJWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.17
• 重原子数：
  33
• 可旋转键数：
  5
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  109
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (5'S,8R)-N-benzoyl-O3'-(tert-butyldimethylsilyl)-5',8-cyclo-7,8-dihydro-2'-deoxyadenosine 在 四氯苯醌 作用下， 以 邻二甲苯 为溶剂， 反应 0.33h， 以90%的产率得到N⁶-benzoyl-3'-O-(tert-butyldimethylsilyl)-5',8-cyclo-5'-oxo-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：

  N-benzoyl-O3'-(tert-butyldimethylsilyl)-5'-oxo-2'-deoxyadenosine 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 氟苯 为溶剂， 反应 2.0h， 生成 (5'S,8R)-N-benzoyl-O3'-(tert-butyldimethylsilyl)-5',8-cyclo-7,8-dihydro-2'-deoxyadenosine 、 N-苯甲酰-2'-脱氧-3'-O-(1,1-二甲基乙基)二甲基硅氧基-腺苷 、 (5'S)-N⁵-benzoyl-3'-O-(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

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.