1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[[(E)-2-[(2R,3S,5R)-3-[tert-butyl(diphenyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]ethenyl]-methoxyphosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione | 289711-56-4

• 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: 1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[[(E)-2-[(2R,3S,5R)-3-[tert-butyl(diphenyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]ethenyl]-methoxyphosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 289711-56-4
• 化学式: C₄₄H₆₁N₄O₁₁PSi₂
• 分子量: 909.133
• InChiKey: MUKXRNFARTUBIR-NUFMOGCYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.98
• 重原子数：
  62
• 可旋转键数：
  16
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  171
• 氢给体数：
  2
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[[(E)-2-[(2R,3S,5R)-3-[tert-butyl(diphenyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]ethenyl]-methoxyphosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione 在 氢氟酸 作用下， 以 乙腈 为溶剂， 以73%的产率得到
  参考文献：
  名称：

  Commercially Available 5‘-DMT Phosphoramidites as Reagents for the Synthesis of Vinylphosphonate-Linked Oligonucleic Acids

  摘要：

  [GRAPHICS]Commercially available cyanoethyl phosphoramidites derived from T, d(C), d(A), and d(G) were hydrolyzed (1H-tetrazole, MeCN/H2O) to give the corresponding H-phosphonates in excellent yields. Palladium(0)-catalyzed cross-coupling of each of these with the thymidine-derived vinylbromide 2 afforded the corresponding vinylphosphonate-linked dimers T*T, d(C)*T, d(A)*T, and d(G)*T in modest to good yields. The T*T dimer was further elaborated to give a 5'-DMT-T*T-3'-CEP building block, and this was used in the automated synthesis of the TpT*TpT tetramer.

  DOI：

  10.1021/ol0166045
• 作为产物：
  描述：

  1-(2-deoxy-3-O-tert-butyldiphenylsilyl-β-D-erythro-pentadialdo-1,4-furanosyl)-5-methyluracil 在 palladium diacetate 三乙胺 、 亚磷酸二甲酯 、 三苯基膦 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 20.0h， 生成 1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[[(E)-2-[(2R,3S,5R)-3-[tert-butyl(diphenyl)silyl]oxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]ethenyl]-methoxyphosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
  参考文献：
  名称：

  A Novel Palladium-Catalysed Coupling Strategy for the Rapid Synthesis of Nucleic Acid Analogues Bearing Modified Backbones

  摘要：

  DOI：

  10.1055/s-1999-2767

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).
• A Novel Palladium-Catalysed Coupling Strategy for the Rapid Synthesis of Nucleic Acid Analogues Bearing Modified Backbones
  作者：Sahar Abbas、Christopher J. Hayes

  DOI：10.1055/s-1999-2767

  日期：1999.7
• Commercially Available 5‘-DMT Phosphoramidites as Reagents for the Synthesis of Vinylphosphonate-Linked Oligonucleic Acids
  作者：Sahar Abbas、Richard D. Bertram、Christopher J. Hayes

  DOI：10.1021/ol0166045

  日期：2001.10.1

  [GRAPHICS]Commercially available cyanoethyl phosphoramidites derived from T, d(C), d(A), and d(G) were hydrolyzed (1H-tetrazole, MeCN/H2O) to give the corresponding H-phosphonates in excellent yields. Palladium(0)-catalyzed cross-coupling of each of these with the thymidine-derived vinylbromide 2 afforded the corresponding vinylphosphonate-linked dimers T*T, d(C)*T, d(A)*T, and d(G)*T in modest to good yields. The T*T dimer was further elaborated to give a 5'-DMT-T*T-3'-CEP building block, and this was used in the automated synthesis of the TpT*TpT tetramer.