2-cyanoethyl 5'-O-dimethoxytrityl-N⁶-benzoyldeoxyadenosin-3'-yl phosphonate | 119484-01-4

• 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: 2-cyanoethyl 5'-O-dimethoxytrityl-N⁶-benzoyldeoxyadenosin-3'-yl phosphonate
• 英文别名: O-2-cyanoethyl 5'-O-dimethoxytrityl-N⁶-benzoyldeoxyadenosin-3'-yl phosphonate；2-cyanoethyl 5'-O-dimethoxytrityl-N⁶-benzoyldeoxyadenosine 3'-phosphonate；5'-O-(4,4'-dimethoxytrityl)-N-benzoyl-adenosine-3'-O-(2-cyanoethyl) H-phosphonate；N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-(2-cyanoethoxyphosphonoyloxy)oxolan-2-yl]purin-6-yl]benzamide
• CAS: 119484-01-4
• 化学式: C₄₁H₃₉N₆O₈P
• 分子量: 774.77
• InChiKey: IPRPTAUFOAUVKC-LIVOIKKVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  56
• 可旋转键数：
  16
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  169
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2-cyanoethyl 5'-O-dimethoxytrityl-N⁶-benzoyldeoxyadenosin-3'-yl phosphonate 在 咪唑 作用下， 以 甲醇 为溶剂， 反应 72.0h， 以76%的产率得到N6-苯甲酰基-5'-O-(4,4'-二甲氧基三苯基)-2'-脱氧腺苷
  参考文献：
  名称：

  Facile methods to recycle nucleosides during solid phase synthesis of oligonucleotides

  摘要：

  Solid phase syntheses of oligonucleotides, using nucleoside phosphoramidites or methylphosphonamidites require a large excess of nucleoside monomers over the hydroxy functions of the growing oligonucleotide chain bound onto the solid phase. The outlined method allows to recover the excess nucleosides. All the protective groups on the sugar and the nucleobase of the monomers are maintained throughout the recycling process.

  DOI：

  10.1016/s0040-4039(00)76822-5
• 作为产物：
  描述：

  N6-苯甲酰基-5'-O-(4,4'-二甲氧基三苯基)-2'-脱氧腺苷 在 N-甲基咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 生成 2-cyanoethyl 5'-O-dimethoxytrityl-N⁶-benzoyldeoxyadenosin-3'-yl phosphonate
  参考文献：
  名称：

  Nucleoside Phosphite,O-Bis(1,1,1,3,3,3-hexafluoro-2-propyl) Deoxyribonucleosid-3′-yl Phosphites. A Versatile Synthetic Intermediate for Phosphonate Modified Nucleotide and Oligonucleotide Synthesis

  摘要：

  O-bis(1,1,1,3,3,3-六氟-2-丙基)脱氧核糖核苷-3′-基磷酸酯单元可以转化为O-核糖核苷-3′-基磷酸酯、O-2-氰乙基O-核糖核苷-3′-基磷酸酯和O-1,1,1,3,3,3-六氟-2-丙基O-核糖核苷-3′-基磷酸硫酸酯。在MeIm存在下，磷酸酯单元与3′-O-苯甲酰胸苷反应生成双胸苷酸衍生物。

  DOI：

  10.1246/cl.1992.935

文献信息

• 2-cyanoethyl nucleoside 3′-phosphonates as a novel starting materials for oligonucleotide synthesis
  作者：Takeshi Wada、Hitoshi Hotoda、Mitsuo Sekine、Tsujiaki Hata

  DOI：10.1016/s0040-4039(00)80439-6

  日期：1988.1

  corresponding phosphorochloridites by use of tris(2, 4, 6-tribromophenoxy) dichlorophosphorane (BDCP) as a chlorinating reagent. The reaction was found to be applicable to the rapid and practical synthesis of oligonucleotides.

  通过使用三（2，4，6,6-三溴苯氧基）二氯磷烷（BDCP）作为氯化试剂，将包括烷基核苷3'-膦酸酯在内的各种二取代膦酸酯迅速转化为相应的次氯代磷酸酯。发现该反应适用于寡核苷酸的快速和实用合成。
• Solution-Phase Synthesis of Branched DNA Hybrids via <i>H</i>-Phosphonate Dimers
  作者：Arunoday Singh、Mariyan Tolev、Christine I. Schilling、Stefan Bräse、Helmut Griesser、Clemens Richert

  DOI：10.1021/jo202508n

  日期：2012.3.16

  method for the solution-phase synthesis of branched oligonucleotides with tetrahedral or pseudo-octahedral geometry is described that involves the coupling of 3′-H-phosphonates of protected dinucleoside phosphates and organic core molecules. The dimer building blocks are produced by a synthesis that requires no chromatographic purification and that produces the dimer H-phosphonates in up to 44% yield

  描述了一种溶液相合成具有四面体或伪八面体几何形状的分支寡核苷酸的方法，该方法包括将被保护的二核苷磷酸酯的3'- H-膦酸酯与有机核心分子偶联。二聚体结构单元是通过不需要色谱纯化的合成方法生产的，并且在不到三天的实验室工作中即可产生高达44％的H-膦酸酯二聚体。总共准备了七个不同的分支杂种，包括序列（CG）4 TBA的新杂种，其中TBA代表四（对-羟基联苯）金刚烷，它通过添加MgCl 2从微摩尔水溶液组装成一种材料。
• SOLID PHASE OLIGONUCLEOTIDE SYNTHESIS BY USING β-CE<i>H</i>-PHOSPHONATE APPROACH
  作者：Kamlesh J. Padiya、Nikhil U. Mohe、Manikrao M. Salunkhe

  DOI：10.1081/scc-120002704

  日期：2002.1.1

  ABSTRACT A new approach to the solid phase synthesis of oligonucleotide is described, which is based on oxidative coupling of nucleoside 3′-β-CE H-phosphonates in presence of N-Bromosuccinimide (NBS) as a coupling agent.

  摘要描述了一种寡核苷酸固相合成的新方法，该方法基于在 N-溴代琥珀酰亚胺 (NBS) 作为偶联剂存在下核苷 3'-β-CE H-膦酸酯的氧化偶联。
• Nonoxidative chlorination of dialkyl phosphonates to dialkyl phosphorochloridites. A new approach to oligonucleotide synthesis
  作者：Takeshi Wada、Ryohei Kato、Tsujiaki Hata

  DOI：10.1021/jo00003a056

  日期：1991.2

  Several dialkyl phosphonates and alkyl nucleoside 3'-phosphonates were transformed into the corresponding highly reactive phosphorochloridites without oxidation of phosphorus by use of tris(2,4,6-tribromophenoxy)-dichlorophosphorane (BDCP) as a chlorinating reagent. The reaction was applied to internucleotidic bond formation. 2-Cyanoethyl and methyl nucleoside 3'-phosphonates were prepared in high yields and were stable enough to be used as starting materials in oligonucleotide synthesis. Examination of dodecathymidylate synthesis on a polymer support, using 2-cyanoethyl or methyl nucleoside 3'-phosphonate as building blocks, showed that the 2-cyanoethyl nucleoside 3'-phosphonate was more effective.
• 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.