Dithiophosphoric acid O-[(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethyl] ester O'-[(2R,3S,5R)-2-hydroxymethyl-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester | 126094-32-4

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: Dithiophosphoric acid O-[(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethyl] ester O'-[(2R,3S,5R)-2-hydroxymethyl-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester
• 英文别名: 1-[(2R,4S,5R)-4-hydroxy-5-[[[(2R,3S,5R)-2-(hydroxymethyl)-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-sulfanylphosphinothioyl]oxymethyl]oxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 126094-32-4
• 化学式: C₂₀H₂₇N₄O₁₀PS₂
• 分子量: 578.561
• InChiKey: UFEVDLJUCSKNPA-KPRKPIBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  209
• 氢给体数：
  5
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  Dithiophosphoric acid O-[(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethyl] ester O'-[(2R,3S,5R)-2-hydroxymethyl-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester 在 1,2-环氧丁烷 作用下， 以 乙醇 为溶剂， 反应 3.0h， 生成 胸苷酰(3'->5')胸苷铵盐
  参考文献：
  名称：

  Synthesis of Oligo(Deoxyribonucleoside Phosphorodithioate)s by the Dithiaphospholane Approach

  摘要：

  A novel method of synthesis of oligo(deoxyribonucleoside phosphorodithioate)s (S-2-ODNs), based on the ring-opening condensation of nucleoside 3'-0-(2-thiono-1,3,2-dithiaphospholane)s with 5'-O-deprotected nucleosi(ti)des in the presence of a strong organic base such as DBU, is presented. The process has been adapted to the requirements of automated solid-phase oligonucleotide synthesis with a relatively short condensation step (5 min) and reasonable step-yield(>95%). N-Methylpyrrolidin-2-ylidenyl (Pya) was found to be the group of choice for the protection of reactive aminofunctions of nucleobases in nucleotide substrates. Sarcosine-containing linker (LCA CPG SAR) was employed due to its known resistance to cleavage by DBU. Several medium-size S-2-ODNs were prepared by this approach. Their identity and purity was confirmed by means of P-31 NMR, gel electrophoresis, and mass spectrometry. It has been demonstrated that, contrary to a recent report, S-2-ODNs are not degraded by DNaseI.

  DOI：

  10.1021/jo00126a060
• 作为产物：
  描述：

  5'-O-pixylthymidine 在 1H-1,2,4-三唑 、 盐酸 、 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 ammonium hydroxide 、 硫化氢 、 三甲基乙酰氯 、 三乙胺 、 三氯化磷 作用下， 反应 4.83h， 生成 Dithiophosphoric acid O-[(2R,3S,5R)-3-hydroxy-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-2-ylmethyl] ester O'-[(2R,3S,5R)-2-hydroxymethyl-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester
  参考文献：
  名称：

  核苷膦二硫代磷酸酯作为制备二核苷二硫代磷酸酯和硫代磷酸酯的中间体

  摘要：

  5'- O-（9-苯基黄嘌呤-9-基）胸腺嘧啶核苷（）以高收率转化成其3'-膦二硫代磷酸酯（）的三乙铵盐；后者化合物被转化为二核苷硫代磷酸酯（），并因此以良好的总收率转化为二核苷二硫代磷酸酯（）。

  DOI：

  10.1016/s0040-4039(01)80782-6

文献信息

• Synthesis of oligonucleoside phosphorodithioates by the H -phosphonothioate method
  作者：Kazuo Kamaike、Kumi Hirose、Yoshihiro Kayama、Etsuko Kawashima

  DOI：10.1016/j.tetlet.2004.06.025

  日期：2004.7

  The phosphorodithioate octamer [(TpS2)7T] was efficiently synthesized using bis(2,6-dimethylphenyl) phosphorochloridate as a coupling agent by application of the H-phosphonothioate method, where oxidation was facilitated using elemental sulfur following completion of oligonucleoside H-phosphonothioates assembly, as with the standard H-phosphonate method.

  使用双（2,6-二甲基苯基）氯代磷酸酯作为偶合剂，通过应用H-磷酸硫代磷酸酯方法，有效地合成了二硫代磷酸酯八聚体[（TpS 2）7 T] ，其中在寡核苷H-完成后，使用元素硫促进了氧化。硫代磷酸酯的组装，与标准的H-膦酸酯方法相同。
• Deoxynucleoside phosphorodithioates. Preparation by a triester method
  作者：Bjarne H. Dahl、Kirsten Bjerg»rde、John Nielsen、Otto Dahl

  DOI：10.1016/s0040-4039(00)97430-6

  日期：1990.1

  A series of active esters of dithiophosphoric acid (3) have been prepared and their properties as potential precursors for dideoxynucleoside phosphorodithioates evaluated.

  已经制备了一系列二硫代磷酸的活性酯（3），并评估了它们作为二脱氧核苷二硫代磷酸酯的潜在前体的性能。
• A new method for the formation of the P–F bond
  作者：Martin Bollmark、Jacek Stawinski

  DOI：10.1039/a701728f

  日期：——

  Iodine-promoted desulfurization of phosphorothioate and phosphorodithioate diesters in the presence of triethylamine tris(hydrofluoride) (TAF) furnish a rapid and quantitative formation of the corresponding phosphorofluoridates and phosphorofluoridothioates; under the reaction conditions phosphoroselenoate and phosphoroselenothioate diesters undergo deselenization affording the phosphorofluoridate and phosphorofluoridothioate diesters, respectively.

  在三乙胺三（氢氟化物）（TAF）存在下，碘促进硫代磷酸酯和二硫代磷酸酯的脱硫反应，快速定量地生成相应的氟代磷酸酯和硫代磷酸酯；在反应条件下，硒代磷酸酯和硫代磷酸酯发生脱硒反应，分别生成氟代磷酸酯和硫代磷酸酯。
• New Methods for the Formation of the P-N and P-F Bonds, their Relevance to Nucleotide and Oligonucleotide Analogues Synthesis
  作者：Inger Kers、Martin Bollmark、Adam Kraszewski、Jacek Stawinski

  DOI：10.1080/10426509908546325

  日期：1999.1.1

  appropriate amines. Also, a new, convenient entry to nucleoside methylphosphonamidates, consisting of an oxidative coupling of nucleoside 3'-methylphosphinates with 5'-aminonucleosides, was investigated. Finally, iodine promoted desulfurization or deselenization of the appropriate phosphorothioate and phosphoroselenoate diesters in the presence of fluoride anion, was found to provide new means for the formation

  已经开发了两种方法来形成氨基磷酸酯，其中氮原子位于核苷酸间键的桥接位置。其中一种使用 H-膦酰胺酸酯作为中间体，另一种基于 H-膦酸酯单酯或其类似物与适当胺的氧化偶联。此外，研究了一种新的、方便的核苷甲基膦酰胺酸盐，由核苷 3'-甲基次膦酸盐与 5'-氨基核苷的氧化偶联组成。最后，发现碘在氟阴离子存在下促进了适当的硫代磷酸酯和硒代磷酸二酯的脱硫或脱硒，为形成 PF 键提供了新的手段。
• PORRITT, GEOFFREY M.;REESE, COLIN B., TETRAHEDRON LETT., 30,(1989) N5, C. 4713-4716
  作者：PORRITT, GEOFFREY M.、REESE, COLIN B.

  DOI：——

  日期：——