5'-O-(tertbutyldimethylsilyl)-α-thymidine-3'-O-(2-cyanoethyl)-H-phosphonate

• 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'-O-(tertbutyldimethylsilyl)-α-thymidine-3'-O-(2-cyanoethyl)-H-phosphonate
• 英文别名: 3-[[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-oxidophosphaniumyl]oxypropanenitrile
• 化学式: C₁₉H₃₂N₃O₇PSi
• 分子量: 473.538
• InChiKey: UUHBEFHWTLDLGB-ARFHVFGLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.79
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  133
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  5'-O-(tertbutyldimethylsilyl)-α-thymidine-3'-O-(2-cyanoethyl)-H-phosphonate 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 palladium diacetate 、 三苯基膦 、 methyloxirane 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 31.0h， 生成 3-[[(2R,3S,5R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-[(E)-2-[(2R,3S,5R)-3-[tert-butyl(diphenyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]ethenyl]-oxidophosphaniumyl]oxypropanenitrile
  参考文献：
  名称：

  An Olefin Cross-Metathesis Approach to Vinylphosphonate-Linked Nucleic Acids

  摘要：

  [GRAPHICS]The synthesis of vinylphosphonate-linked nucleotide dimers has been achieved using an olefin cross-metathesis (CM) reaction as a key step. The 1,3-dimesityl-4,5-dihydroimidazol-2-ylidine-containing catalyst 5 (Grubbs' second-generation catalyst) was found to be the superior catalyst for this transformation. Both metathesis partners were readily available using known methodology, and the vinylphosphonate-linked dimer was produced with high levels of (E)-selectivity (> 20:1) in 58% yield (70% based on recovered starting material).

  DOI：

  10.1021/ol016366d

文献信息

• An improved procedure for the synthesis of vinylphosphonate-linked nucleic acids
  作者：Sahar Abbas、Christopher J Hayes

  DOI：10.1016/s0040-4039(00)00653-5

  日期：2000.6

  The syntheses of a range of 5′-deoxy-5′-methylidene phosphonate-containing thymidine dimers have been achieved using a palladium-catalysed cross coupling reaction as a key step. The optimised reaction conditions comprising of palladium acetate, 1,1′-bis(diphenylphosphino)ferrocene and propylene oxide in THF were found to couple a range of H-phosphonates and vinyl bromide 3 in fair to excellent yield

  使用钯催化的交叉偶联反应作为关键步骤，已经实现了一系列含5'-脱氧-5'-亚甲基膦酸酯的胸苷二聚体的合成。发现在THF中由乙酸钯，1，1'-双（二苯基膦基）二茂铁和环氧丙烷组成的最优化反应条件公平地将一系列H-膦酸酯和乙烯基溴3偶联至优异的收率。
• An Olefin Cross-Metathesis Approach to Vinylphosphonate-Linked Nucleic Acids
  作者：Manuel Lera、Christopher J. Hayes

  DOI：10.1021/ol016366d

  日期：2001.8.1

  [GRAPHICS]The synthesis of vinylphosphonate-linked nucleotide dimers has been achieved using an olefin cross-metathesis (CM) reaction as a key step. The 1,3-dimesityl-4,5-dihydroimidazol-2-ylidine-containing catalyst 5 (Grubbs' second-generation catalyst) was found to be the superior catalyst for this transformation. Both metathesis partners were readily available using known methodology, and the vinylphosphonate-linked dimer was produced with high levels of (E)-selectivity (> 20:1) in 58% yield (70% based on recovered starting material).