(3'S,5'R,6'R)-1-[2'-deoxy-6'-(trifluoroacetamido)-3',5'-ethano-β-D-ribofuranosyl]thymine | 258505-07-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3'S,5'R,6'R)-1-[2'-deoxy-6'-(trifluoroacetamido)-3',5'-ethano-β-D-ribofuranosyl]thymine
• 英文别名: N-[(2R,3aS,5R,6R,6aR)-3a,6-dihydroxy-2-(5-methyl-2,4-dioxopyrimidin-1-yl)-2,3,4,5,6,6a-hexahydrocyclopenta[b]furan-5-yl]-2,2,2-trifluoroacetamide
• CAS: 258505-07-6
• 化学式: C₁₄H₁₆F₃N₃O₆
• 分子量: 379.293
• InChiKey: WBWSNWFTGDEUPJ-OJMIUMIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.32
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  133.65
• 氢给体数：
  4.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (3'S,5'R,6'R)-1-[2'-deoxy-6'-(trifluoroacetamido)-3',5'-ethano-β-D-ribofuranosyl]thymine 在 氨 作用下， 以 甲醇 为溶剂， 反应 0.75h， 以98%的产率得到(3'S,5'R,6'R)-1-(6'-amino-2'-deoxy-3',5'-ethano-β-D-ribofuranosyl)thymine
  参考文献：
  名称：

  Nucleic-Acid Analogs with Restricted Conformational Flexibility in the Sugar-Phosphate Backbone (`Bicyclo-DNA'), Part 7, Synthesis and Properties of Oligodeoxynucleotides Containing [(3′S,5′S,6′R)-6′-Amino-2′-deoxy-3′,5′-ethano-β-D-ribofuranosyl]thymine (=(6′R)-6′-Amino-bicyclo-thymidine)

  摘要：

  We describe the synthesis of the acetamido- and trifluoroacetamido-functionalized bicyclo-thymidines 11 and 12, starting from the silyl enol ether 1, in 6 steps. These nucleosides were converted to the corresponding cyanoethyl phosphoramidite building blocks 16 and 17 and subsequently incorporated into the homothymidylate decamers 18-22. Upon deprotection of the oligomers, the trifluoroacetamido functions were cleaved, leaving behind a free amino function in the sugar-phosphate backbone that is protonated at neutral pH, giving rise to partially zwitterionic oligonucleotides. Pairing properties with the complementary DNA oligomer d(A(10)), as determined by UV/melting curves, revealed a slightly increased stability of the duplex d(A(10)) . 20, in which the decathymidylate sequence shows an alternating arrangement of natural thymidine and amino-bicyclo-thymidine residues, relative to the natural reference duplex. The dependence of T-m on the salt concentration of the medium is reduced in this case. Duplex destabilization occurs if the amino-bicyclo-thymidine residues are replaced by the charge-neutral acetamido-bicyclo-nucleosides (e.g., d(A(10)) . 22), most probably due to steric interference of the acetamido substituent with the backbone P-O(5') bond.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1813::aid-hlca1813>3.0.co;2-0
• 作为产物：
  描述：

  N-{(1R,3S,5S,7R,8R)-8-{[(tert-butyl)dimethylsilyl]oxy}-5-hydroxy-3-methoxy-2-oxabicyclo[3.3.0]octan-7-yl}-2,2,2-trifluoroacetate 在 三甲基氯硅烷 、 N,O-双三甲硅基乙酰胺 、 三氟甲磺酸三甲基硅酯 、 四丁基氟化铵 、 溶剂黄146 作用下， 以 乙腈 为溶剂， 反应 25.0h， 生成 (3'S,5'R,6'R)-1-[2'-deoxy-6'-(trifluoroacetamido)-3',5'-ethano-β-D-ribofuranosyl]thymine
  参考文献：
  名称：

  Nucleic-Acid Analogs with Restricted Conformational Flexibility in the Sugar-Phosphate Backbone (`Bicyclo-DNA'), Part 7, Synthesis and Properties of Oligodeoxynucleotides Containing [(3′S,5′S,6′R)-6′-Amino-2′-deoxy-3′,5′-ethano-β-D-ribofuranosyl]thymine (=(6′R)-6′-Amino-bicyclo-thymidine)

  摘要：

  We describe the synthesis of the acetamido- and trifluoroacetamido-functionalized bicyclo-thymidines 11 and 12, starting from the silyl enol ether 1, in 6 steps. These nucleosides were converted to the corresponding cyanoethyl phosphoramidite building blocks 16 and 17 and subsequently incorporated into the homothymidylate decamers 18-22. Upon deprotection of the oligomers, the trifluoroacetamido functions were cleaved, leaving behind a free amino function in the sugar-phosphate backbone that is protonated at neutral pH, giving rise to partially zwitterionic oligonucleotides. Pairing properties with the complementary DNA oligomer d(A(10)), as determined by UV/melting curves, revealed a slightly increased stability of the duplex d(A(10)) . 20, in which the decathymidylate sequence shows an alternating arrangement of natural thymidine and amino-bicyclo-thymidine residues, relative to the natural reference duplex. The dependence of T-m on the salt concentration of the medium is reduced in this case. Duplex destabilization occurs if the amino-bicyclo-thymidine residues are replaced by the charge-neutral acetamido-bicyclo-nucleosides (e.g., d(A(10)) . 22), most probably due to steric interference of the acetamido substituent with the backbone P-O(5') bond.

  DOI：

  10.1002/(sici)1522-2675(19991110)82:11<1813::aid-hlca1813>3.0.co;2-0