1,8-diazabicyclo[5.4.0]undec-7-enium 5'-O-(4,4'-dimethoxytrityl)deoxyadenosin-3'-yl phosphonate | 145432-04-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: 1,8-diazabicyclo[5.4.0]undec-7-enium 5'-O-(4,4'-dimethoxytrityl)deoxyadenosin-3'-yl phosphonate
• CAS: 145432-04-8
• 化学式: C₉H₁₆N₂*C₃₁H₃₂N₅O₇P
• 分子量: 769.838
• InChiKey: LLFAIPGNUHTHBJ-QPCDWQCMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.15
• 重原子数：
  55.0
• 可旋转键数：
  11.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  168.67
• 氢给体数：
  2.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  1,8-diazabicyclo[5.4.0]undec-7-enium 5'-O-(4,4'-dimethoxytrityl)deoxyadenosin-3'-yl phosphonate 在 双(三甲基硅基)过氧化物 、 三氟甲磺酸三甲基硅酯 、 N,O-bis(trimethylsilyl)benzamide 作用下， 以 二氯甲烷 为溶剂， 反应 4.0h， 以97%的产率得到O^5'-(4,4'-dimethoxy-trityl)-2'-deoxy-[3']adenylic acid
  参考文献：
  名称：

  A Facile Method for the Oxidation of Nucleoside H-Phosphonates to Phosphates with Bis(trimethylsilyl) Peroxide

  摘要：

  我们开发了一种便捷的方法，在催化剂三甲基硅基三氟甲磺酸酯的作用下，用双（三甲基硅基）过氧化物和N，O-双（三甲基硅基）乙酰胺实现核苷H-膦酸单酯和二酯的氧化。

  DOI：

  10.1055/s-1999-2951
• 作为产物：
  描述：

  N⁶-(dimethylamino-methylene)-2'-deoxy-adenosine 在 吡啶 作用下， 生成 1,8-diazabicyclo[5.4.0]undec-7-enium 5'-O-(4,4'-dimethoxytrityl)deoxyadenosin-3'-yl phosphonate
  参考文献：
  名称：

  无氨基保护的H-膦酸酯DNA合成

  摘要：

  通过H-膦酸酯法合成DNA不需要使用氨基保护基。胞嘧啶氨基和鸟嘌呤06 / N1位置确实会与缩合剂反应，但是这些衍生物会在标准氨水条件下裂解，该条件通常用于从固相支持物中分解和裂解寡核苷酸。

  DOI：

  10.1016/s0040-4039(00)61075-4

文献信息

• First synthesis of H-phosphonate oligonucleotides bearing N-unmodified bases
  作者：Takeshi Wada、Fumio Honda、Yuichi Sato、Mitsuo Sekine

  DOI：10.1016/s0040-4039(98)02481-2

  日期：1999.1

  H-phosphonate internucleotidic linkages and unmodified nucleobases were synthesized for the first time by the new H-phosphonate method using N-unprotected monomers. The 6-hydroxyhexyl phosphonates at both the 5′ and 3′ ends were found to be highly effective for stabilization of the H-phosphonate oligonucleotides. Solid-phase synthesis of H-phosphonate oligodeoxy-ribonucleotides containing dA, dC, dG,

  利用N-未保护的单体，通过新的H-膦酸酯方法首次合成了带有H-膦酸酯核苷酸间键和未修饰核碱基的寡脱氧核糖核苷酸。发现在5'和3'端的6-羟基己基膦酸酯对于稳定H-膦酸酯寡核苷酸是高度有效的。实现了含有dA，dC，dG和T的H-膦酸酯寡脱氧核糖核苷酸的固相合成。
• Chemical Synthesis of Oligodeoxyribonucleotides Using <i>N</i>-Unprotected <i>H</i>-Phosphonate Monomers and Carbonium and Phosphonium Condensing Reagents:  <i>O</i>-Selective Phosphonylation and Condensation
  作者：Takeshi Wada、Yuichi Sato、Fumio Honda、Shun-ichi Kawahara、Mitsuo Sekine

  DOI：10.1021/ja9726015

  日期：1997.12.1

  Oligodeoxyribonucleotides were synthesized using H-phosphonate monomers without amino protection. The H-phosphonate monomers of deoxyadenosine, deoxycytidine, and deoxyguanosine bearing the free amino groups were synthesized in good yields by O-selective phosphonylation of the parent 5'-O-(dimethoxytrityl)deoxyribonucleosides. It was found that the amino groups of the nucleosides were not modified during internucleotidic bond formation where (benzotriazol-1-yloxy)carbonium and -phosphonium compounds were employed as condensing reagents. The most effective condensing reagent for rapid internucleotidic bond formation was found to be 2-(benzotriazol-1-yloxy)-1,1-dimethyl-2-hexafluorophosphate (BOMP). In the present H-phosphonate method, 2-(phenylsulfonyl)-3-(3-nitrophenyl)oxaziridine (PNO) was employed as a new oxidizing reagent for the oxidation of internucleotidic H-phosphonate linkages under anhydrous conditions in the presence of N,O-bis(trimethylsilyl)acetamide. The reaction mechanism for the O-selective condensation was investigated in detail by means of P-31 NMR spectroscopy. Unprecedented oxidation of the H-phosphonate monomers was observed during activation of the monomers with (benzotriazol-1-yloxy)phosphonium and -carbonium condensing reagents in the absence of the 5'-hydroxyl components. A mechanism for the O-selective condensation was proposed on the basis of ab initio molecular orbital calculations for the model compounds at the HF/6-31G* level.