[(2R,3S,5R)-2-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-hydroxyphosphinothioyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate | 118149-31-8

• 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: [(2R,3S,5R)-2-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-hydroxyphosphinothioyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate
• CAS: 118149-31-8
• 化学式: C₄₃H₄₇N₄O₁₄PS
• 分子量: 906.904
• InChiKey: DCLFBXBFBGFOAR-FSIDXJKQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  63
• 可旋转键数：
  17
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  242
• 氢给体数：
  3
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  [(2R,3S,5R)-2-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-hydroxyphosphinothioyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate 在 ammonium hydroxide 作用下， 反应 16.0h， 生成 1-[(2R,4S,5R)-5-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-hydroxyphosphinothioyl]oxymethyl]-4-hydroxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
  参考文献：
  名称：

  Kumar, Prabhat; Misra, Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 1997, vol. 36, # 11, p. 1000 - 1004

  摘要：

  DOI：
• 作为产物：
  描述：

  5‘-O-dimethoxytrityl-2’-deoxyribothymidine 3‘-O-phosphorodiamidite 在 四氮唑 、 硫化氢 、 碘 作用下， 以 吡啶 、 水 、 乙腈 为溶剂， 反应 16.02h， 生成 [(2R,3S,5R)-2-[[[(2R,3S,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxy-hydroxyphosphinothioyl]oxymethyl]-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-3-yl] acetate
  参考文献：
  名称：

  二核苷二硫代磷酸酯的合成与表征

  摘要：

  二核苷亚磷酰胺，H 2 S和四唑反应形成二核苷H-硫代磷酸酯。用硫氧化产生二硫代磷酸酯。在胺，醇或水的存在下碘氧化可生成硫代磷酸氨基甲酸酯，硫代三酸酯或硫代二酯。

  DOI：

  10.1016/0040-4039(88)85045-7

文献信息

• Thermolytic Properties of 3-(2-Pyridyl)-1-propyl and 2-[<i>N</i>-Methyl-<i>N</i>-(2-pyridyl)]aminoethyl Phosphate/Thiophosphate Protecting Groups in Solid-Phase Synthesis of Oligodeoxyribonucleotides
  作者：Jacek Cieślak、Serge L. Beaucage

  DOI：10.1021/jo0354490

  日期：2003.12.1

  thermolytic phosphate/thiophosphate protecting groups has been investigated. Specifically, 2-pyridinepropanol and 2-[N-methyl-N-(2-pyridyl)]aminoethanol were incorporated into deoxyribonucleoside phosphoramidites 7a-d and 9, which were found as efficient as 2-cyanoethyl deoxyribonucleoside phosphoramidites in solid-phase oligonucleotide synthesis. Whereas the removal of 3-(2-pyridyl)-1-propyl phosphate/thiophosphate

  在固相寡核苷酸合成中，热解基团可以替代传统的2-氰基乙基用于磷酸酯/硫代磷酸酯的保护，以防止在用于寡核苷酸脱保护的基本条件下通过丙烯腈产生的DNA烷基化。另外，在设计用于在诊断微阵列上合成寡核苷酸的“热驱动”过程的背景下，热解基团是有吸引力的。在这些方面，已经研究了吡啶衍生物作为热解磷酸酯/硫代磷酸酯保护基的潜在应用。具体地，将2-吡啶丙醇和2- [N-甲基-N-（2-吡啶基）]氨基乙醇掺入脱氧核糖核苷亚磷酰胺7a-d和9中，在固相寡核苷酸合成中，它们被发现与2-氰基乙基脱氧核糖核苷亚磷酰胺一样有效。在55℃，浓NH4OH或pH 7.0的水性缓冲液中加热30分钟内，从寡核苷酸中除去3-（2-吡啶基）-1-丙基磷酸/硫代磷酸酯保护基。当在寡核苷酸合成过程中形成磷酸或硫代磷酸酯时，N-甲基-N-（2-吡啶基）]氨基乙基会自发出现。这些基团的脱保护遵循环脱酯化过程，产生双环盐13和14作为副产物
• Studies of Asymmetric Induction in the Synthesis of Dinucleoside Phosphorothioates from 2-Oxo-1,3,2-dithiaphospholane Nucleoside Derivatives
  作者：Magdalena Olesiak、Andrzej Okruszek

  DOI：10.1080/10426500902947898

  日期：2009.6.23

  The nucleoside derivatives, containing at 3'-O or 5'-O-position 2-oxo-1,3,2-dithiaphospholane function were found to react in the presence of DBU with a hydroxyl group of appropriately protected nucleosides to yield, after deprotection, dinucleoside phosphorothioates in moderate yields. An asymmetric induction connected with the formation of new chiral phosphorothioate center has been examined.
• O-Methyl-bis-O-(4-nitrophenyl)phosphite: a novel chemoselective O-phosphitylating reagent
  作者：Wojciech Dabkowski、Łucja Kazimierczak

  DOI：10.1016/j.tetlet.2009.06.102

  日期：2009.9

  A novel chemoselective O-phosphitylating reagent containing two aryloxy leaving groups at a P(III) center is developed for selective formation of P(Ill) esters from amino alcohols without the need to protect the amino group. The reagent proved to be highly convenient for the synthesis of dinucleotides, P(III)-F structures, and cyclic P(III) nucleotides. (C) 2009 Elsevier Ltd. All rights reserved.
• Solution Phase Synthesis of Dithymidine Phosphorothioate by a Phosphotriester Method Using New<i>S</i>-Protecting Groups
  作者：Ask Püschl、Jan Kehler、Otto Dahl

  DOI：10.1080/07328319708002529

  日期：1997.1

  A phosphotriester method for the synthesis of dithymidine phosphorothioates with eight S-protecting groups has been investigated. Three of the S-protecting groups possesed catalytic activity, however side reactions occurred under deprotection. The best S-protecting group was 4-chloro-2-nitrobenzyl which could be removed with a minimum of side reactions (0.3%). The Coupling reagent PyFNOP (11) gave protected dithymidine phosphorothioate in 96% yield after 15 min coupling.
• Brill, Wolfgang K.-D.; Nielsen, John; Caruthers, Marvin H., Journal of the American Chemical Society, 1991, vol. 113, # 10, p. 3972 - 3980
  作者：Brill, Wolfgang K.-D.、Nielsen, John、Caruthers, Marvin H.

  DOI：——

  日期：——