1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[methoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione | 236754-86-2

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物
• 英文名称: 1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[methoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 236754-86-2
• 化学式: C₁₇H₃₁N₂O₇PSi
• 分子量: 434.502
• InChiKey: HVFSEKRTLYMAMY-BFHYXJOUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.51
• 重原子数：
  28
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  109
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[methoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione 在 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 以100%的产率得到5’-O-(叔丁基二甲基甲硅烷基)胸苷
  参考文献：
  名称：

  合成乙烯基膦酸酯连接的核酸的改进程序

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(00)00653-5
• 作为产物：
  描述：

  Diisopropyl-phosphoramidous acid (2R,3S,5R)-2-(tert-butyl-dimethyl-silanyloxymethyl)-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl ester methyl ester 在 四氮唑 、 水 作用下， 以 乙腈 为溶剂， 以88%的产率得到1-[(2R,4S,5R)-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-4-[methoxy(oxido)phosphaniumyl]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

• Phosphoramidate synthesis via copper-catalysed aerobic oxidative coupling of amines and H-phosphonates
  作者：Jamie Fraser、Laura J. Wilson、Rebecca K. Blundell、Christopher J. Hayes

  DOI：10.1039/c3cc45680c

  日期：——

  The copper-catalysed oxidative coupling of amines and H-phosphonates to produce phosphoramidates has been achieved using CuI as the catalyst and O2 (present in air) as the sole oxidant.

  铜催化的胺和H-臊酸盐的氧化偶联反应，以生成臊酰胺，已成功实现，使用CuI作为催化剂，并以O2（存在于空气中）作为唯一的氧化剂。
• A New One-Pot Synthesis of Alkynylphosphonates
  作者：Manuel Lera、Christopher J. Hayes

  DOI：10.1021/ol0066173

  日期：2000.11.1

  A method for the palladium-catalyzed synthesis of alkynylphosphonates from 1,1-dibromo-1-alkenes has been developed. In general, the best catalyst system for this transformation was found to be Pd(OAc)(2), dppf, H-phosphonate, propylene oxide, DMF, 80 degrees C. The reaction appears tolerant of a range of functional groups in both the 1,1-dibromo-1-alkene and H-phosphonate coupling partners. The synthesis

  已经开发出一种由1，1-二溴-1-烯烃钯催化合成炔基膦酸酯的方法。通常，发现该转化的最佳催化剂体系是Pd（OAc）（2），dppf，H-膦酸酯，环氧丙烷，DMF，80°C。该反应在两个1,1-二溴-1-烯烃和H-膦酸酯偶联伙伴。骨架修饰的胸苷二聚体的合成用于说明该方法在复杂靶分子合成中的应用。
• 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.
• 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).