1-(5-O-(tert-butyldimethylsilyl)-3-O-(trimethylsilyl)-3-C-cyano-2-deoxy-β-D-threo-pentofuranosyl)thymine | 220928-42-7

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 1-(5-O-(tert-butyldimethylsilyl)-3-O-(trimethylsilyl)-3-C-cyano-2-deoxy-β-D-threo-pentofuranosyl)thymine
• 英文别名: (2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)-3-trimethylsilyloxyoxolane-3-carbonitrile
• CAS: 220928-42-7
• 化学式: C₂₀H₃₅N₃O₅Si₂
• 分子量: 453.686
• InChiKey: MPIIMWQYGPAPGD-QINHECLXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.27
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-(5-O-(tert-butyldimethylsilyl)-3-O-(trimethylsilyl)-3-C-cyano-2-deoxy-β-D-threo-pentofuranosyl)thymine 在 盐酸 、 4-二甲氨基吡啶 、 copper(l) iodide 作用下， 以 吡啶 为溶剂， 反应 56.0h， 生成 1-(5-O-(4,4'-dimethoxytrityl)-3-C-benzoyl-2-deoxy-β-D-threo-pentofuranosyl)thymine
  参考文献：
  名称：

  C-3‘-Branched Thymidines as Precursors for the Selective Generation of C-3‘-Nucleoside Radicals

  摘要：

  C-3'-nucleoside radicals can be generated via Norrish type I photocleavage of C-3'-acyl nucleoside derivatives. In monomer experiments employing C-3'-acylthymidine derivatives 2 and 3, a 1:1 mixture of isomers of the H-abstraction products was obtained when the photolysis was carried out in the presence of a hydrogen donor. Derivatives 2 were synthesized by an approach which involves the formation of a silyl-protected cyanohydrin, which is subsequently alkylated with organolithium reagents, followed by hydrolysis. Derivatives 3 could be obtained via a multistep synthesis starting from diol 7. Several different methods were attempted to oxidize the unprotected diol to the alpha-hydroxy aldehyde. Finally, a route was chosen which involves a protection-deprotection sequence followed by oxidation of the free primary alcohol. The resulting modified nucleosides should facilitate the study of C-3'-DNA radicals.

  DOI：

  10.1021/jo982022y
• 作为产物：
  描述：

  三甲基氰硅烷 、 氰化钾 、 5'-(O-tert-butyl(dimethyl)silyl)-3'-ketothymidine 在 18-冠醚-6 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 1-(5-O-(tert-butyldimethylsilyl)-3-O-(trimethylsilyl)-3-C-cyano-2-deoxy-β-D-threo-pentofuranosyl)thymine 、 1-(5-O-(tert-butyldimethylsilyl)-3-O-(trimethylsilyl)-3-C-cyano-2-deoxy-β-D-erythro-pentofuranosyl)thymine
  参考文献：
  名称：

  C-3‘-Branched Thymidines as Precursors for the Selective Generation of C-3‘-Nucleoside Radicals

  摘要：

  C-3'-nucleoside radicals can be generated via Norrish type I photocleavage of C-3'-acyl nucleoside derivatives. In monomer experiments employing C-3'-acylthymidine derivatives 2 and 3, a 1:1 mixture of isomers of the H-abstraction products was obtained when the photolysis was carried out in the presence of a hydrogen donor. Derivatives 2 were synthesized by an approach which involves the formation of a silyl-protected cyanohydrin, which is subsequently alkylated with organolithium reagents, followed by hydrolysis. Derivatives 3 could be obtained via a multistep synthesis starting from diol 7. Several different methods were attempted to oxidize the unprotected diol to the alpha-hydroxy aldehyde. Finally, a route was chosen which involves a protection-deprotection sequence followed by oxidation of the free primary alcohol. The resulting modified nucleosides should facilitate the study of C-3'-DNA radicals.

  DOI：

  10.1021/jo982022y

文献信息

• C-3‘-Branched Thymidines as Precursors for the Selective Generation of C-3‘-Nucleoside Radicals
  作者：Steffi Körner、Amanda Bryant-Friedrich、Bernd Giese

  DOI：10.1021/jo982022y

  日期：1999.3.1

  C-3'-nucleoside radicals can be generated via Norrish type I photocleavage of C-3'-acyl nucleoside derivatives. In monomer experiments employing C-3'-acylthymidine derivatives 2 and 3, a 1:1 mixture of isomers of the H-abstraction products was obtained when the photolysis was carried out in the presence of a hydrogen donor. Derivatives 2 were synthesized by an approach which involves the formation of a silyl-protected cyanohydrin, which is subsequently alkylated with organolithium reagents, followed by hydrolysis. Derivatives 3 could be obtained via a multistep synthesis starting from diol 7. Several different methods were attempted to oxidize the unprotected diol to the alpha-hydroxy aldehyde. Finally, a route was chosen which involves a protection-deprotection sequence followed by oxidation of the free primary alcohol. The resulting modified nucleosides should facilitate the study of C-3'-DNA radicals.