(5'S)-3'-O-[(tert-butyl)dimethylsilyl]-5'-C-(3-methylbutyl)thymidine | 331822-55-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (5'S)-3'-O-[(tert-butyl)dimethylsilyl]-5'-C-(3-methylbutyl)thymidine
• CAS: 331822-55-0
• 化学式: C₂₁H₃₈N₂O₅Si
• 分子量: 426.629
• InChiKey: IXFHPTNRQHMLEI-WNRNVDISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.32
• 重原子数：
  29.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  93.55
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (5'S)-3'-O-[(tert-butyl)dimethylsilyl]-5'-C-(3-methylbutyl)thymidine 在 ammonium hydroxide 、 四丁基氟化铵 、 三乙胺 、 N,N-二异丙基乙胺 、 三氯氧磷 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 吡啶 、 乙腈 为溶剂， 反应 40.0h， 生成 (5'S)-N⁴-benzoyl-2'-deoxy-5-methyl-5'-C-(3-methylbutyl)-5'-O-(9-phenyl-9H-xanthen-9-yl)cytidine 3'-(2-cyanoethyl diisopropylphosphoramidite)
  参考文献：
  名称：

  Synthesis of (5′S)-5′-C-Alkyl-2′-deoxynucleosides

  摘要：

  We describe the synthesis of (S'S)-5'-C-butylthymidine (5a), of the (S'S)-5'-C-butyl- and the (5'S)-5'-C-isopentyl derivatives 16a and 16b of 2'-deoxy-5-methylcytidine, as well as of the corresponding cyanoethyl phosphoramidites 9a,b and 14a,b, respectively. Starting from thymidin-5'-al 1, the alkyl chain at C(5') is introduced via Wittig chemistry to selectively yield the (Z)-olefin derivatives 3a and 3b (Scheme 2). The secondary OH function at C(5') is then introduced by epoxidation followed by regioselective reduction of the epoxy derivatives 4a and 4b with diisobutylaluminium hydride. In the latter step, a kinetic resolution of the diastereoisomer mixture 4a and 4b occurs, yielding the alkylated nucleoside 2a and 2b, respectively, with (5'S)configuration in high diastereoisomer purity (de=94%). The corresponding 2'-deoxy-5-methylcytidine derivatives are obtained from the protected 5'-alkylated thymidine derivatives 7a and 7b via known base interconversion processes in excellent yields (Scheme 3). Application of the same strategy to the purine nucleoside 2'-deoxyadenine to obtain 5'-C-butyl-2'-deoxyadenosine 25 proved to be difficult due to the sensitivity of the purine base to hydride-based reducing agents (Scheme 4).

  DOI：

  10.1002/1522-2675(20010131)84:1<87::aid-hlca87>3.0.co;2-1
• 作为产物：
  描述：

  3'-tert-butyldimethylsilylthymidine 5'-carboxaldehyde 在 sodium hexamethyldisilazane 、 二异丁基氢化铝 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 95.5h， 生成 (5'S)-3'-O-[(tert-butyl)dimethylsilyl]-5'-C-(3-methylbutyl)thymidine
  参考文献：
  名称：

  Synthesis of (5′S)-5′-C-Alkyl-2′-deoxynucleosides

  摘要：

  We describe the synthesis of (S'S)-5'-C-butylthymidine (5a), of the (S'S)-5'-C-butyl- and the (5'S)-5'-C-isopentyl derivatives 16a and 16b of 2'-deoxy-5-methylcytidine, as well as of the corresponding cyanoethyl phosphoramidites 9a,b and 14a,b, respectively. Starting from thymidin-5'-al 1, the alkyl chain at C(5') is introduced via Wittig chemistry to selectively yield the (Z)-olefin derivatives 3a and 3b (Scheme 2). The secondary OH function at C(5') is then introduced by epoxidation followed by regioselective reduction of the epoxy derivatives 4a and 4b with diisobutylaluminium hydride. In the latter step, a kinetic resolution of the diastereoisomer mixture 4a and 4b occurs, yielding the alkylated nucleoside 2a and 2b, respectively, with (5'S)configuration in high diastereoisomer purity (de=94%). The corresponding 2'-deoxy-5-methylcytidine derivatives are obtained from the protected 5'-alkylated thymidine derivatives 7a and 7b via known base interconversion processes in excellent yields (Scheme 3). Application of the same strategy to the purine nucleoside 2'-deoxyadenine to obtain 5'-C-butyl-2'-deoxyadenosine 25 proved to be difficult due to the sensitivity of the purine base to hydride-based reducing agents (Scheme 4).

  DOI：

  10.1002/1522-2675(20010131)84:1<87::aid-hlca87>3.0.co;2-1