3'-O-(imidazol-1-yl)carbonyl-5'-O-(t-butyl)dimethylsilyl-2'-deoxyadenosine | 1278473-69-0

• 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: 3'-O-(imidazol-1-yl)carbonyl-5'-O-(t-butyl)dimethylsilyl-2'-deoxyadenosine
• 英文别名: 3'-O-(imidazol-1-yl)carbonyl-5'-O-TBDMS-2'-deoxyadenosine；[(2R,3S,5R)-5-(6-aminopurin-9-yl)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-3-yl] imidazole-1-carboxylate
• CAS: 1278473-69-0
• 化学式: C₂₀H₂₉N₇O₄Si
• 分子量: 459.58
• InChiKey: HULNTLRYWQDUIB-RRFJBIMHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.97
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  132
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  5'-O-(tert-butyldimethylsilyl)-2'-deoxyadenosine 、 N,N'-羰基二咪唑 在 potassium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 以76%的产率得到3'-O-(imidazol-1-yl)carbonyl-5'-O-(t-butyl)dimethylsilyl-2'-deoxyadenosine
  参考文献：
  名称：

  Syntheses of Aliphatic Polycarbonates from 2′-Deoxyribonucleosides

  摘要：

  Poly(2'-deoxyadenosine) and poly(thymidine) constructed of carbonate linkages were synthesized by poly-condensation between silyl ether and carbonylimidazolide at the 3'- and 5'-positions of the 2'-deoxyribonucleoside monomers. The N-benzoyl-2'-deoxyadenosine monomer afforded the corresponding polycarbonate together with the cyclic oligomers. However, the deprotection of the N-benzoyl group resulted in the scission of the polymer main chain. Thus, the N-unprotected 2'-deoxyadenosine monomers were examined for polycondensation. However, there was involved the undesired reaction between the adenine amino group and the carbonylimidazolide to form the carbamate linkage. In order to exclude this unfavorable reaction, dynamic protection was employed. Strong hydrogen bonding was used in place of the usual covalent bonding for reducing the nucleophilicity of the adenine amino group. Herein, 3',5'-O-diacylthymidines that form the complementary hydrogen bonding with the adenine amino group were added to the polymerization system of the N-unprotected 2'-deoxyadenosine monomer. Consequently, although the oligomers (M-n = 1000-1500) were produced, the contents of the carbamate group were greatly reduced. The dynamic protection reagents were easily and quantitatively recovered as the MeOH soluble parts from the polymerization mixtures. In the polycondensation of the thymidine monomer, there tended to be involved another unfavorable reaction of carbonate exchange, which consequently formed the irregular carbonate linkages at not only the but also the 3'-3' and positions. Employing the well-designed monomer suppressed the carbonate exchange reaction to produce poly(thymidine) with the almost regular 3'-5'carbonate linkages.

  DOI：

  10.1021/bm101328j

文献信息

• Syntheses of Aliphatic Polycarbonates from 2′-Deoxyribonucleosides
  作者：Masato Suzuki、Toyokazu Sekido、Shin-ichi Matsuoka、Koji Takagi

  DOI：10.1021/bm101328j

  日期：2011.5.9

  Poly(2'-deoxyadenosine) and poly(thymidine) constructed of carbonate linkages were synthesized by poly-condensation between silyl ether and carbonylimidazolide at the 3'- and 5'-positions of the 2'-deoxyribonucleoside monomers. The N-benzoyl-2'-deoxyadenosine monomer afforded the corresponding polycarbonate together with the cyclic oligomers. However, the deprotection of the N-benzoyl group resulted in the scission of the polymer main chain. Thus, the N-unprotected 2'-deoxyadenosine monomers were examined for polycondensation. However, there was involved the undesired reaction between the adenine amino group and the carbonylimidazolide to form the carbamate linkage. In order to exclude this unfavorable reaction, dynamic protection was employed. Strong hydrogen bonding was used in place of the usual covalent bonding for reducing the nucleophilicity of the adenine amino group. Herein, 3',5'-O-diacylthymidines that form the complementary hydrogen bonding with the adenine amino group were added to the polymerization system of the N-unprotected 2'-deoxyadenosine monomer. Consequently, although the oligomers (M-n = 1000-1500) were produced, the contents of the carbamate group were greatly reduced. The dynamic protection reagents were easily and quantitatively recovered as the MeOH soluble parts from the polymerization mixtures. In the polycondensation of the thymidine monomer, there tended to be involved another unfavorable reaction of carbonate exchange, which consequently formed the irregular carbonate linkages at not only the but also the 3'-3' and positions. Employing the well-designed monomer suppressed the carbonate exchange reaction to produce poly(thymidine) with the almost regular 3'-5'carbonate linkages.