bis(O-4-nitrophenyl)-N,N-diisopropylphosphoramidite | 153413-65-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(O-4-nitrophenyl)-N,N-diisopropylphosphoramidite
• 英文别名: N-bis(4-nitrophenoxy)phosphanyl-N-propan-2-ylpropan-2-amine
• CAS: 153413-65-1
• 化学式: C₁₈H₂₂N₃O₆P
• 分子量: 407.363
• InChiKey: LKRAIDXMRIKPIY-UHFFFAOYSA-N

物化性质

• 熔点：
  120-122 °C
• 沸点：
  507.5±60.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  113
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  bis(O-4-nitrophenyl)-N,N-diisopropylphosphoramidite 在 四丁基氟化铵 作用下， 以 乙腈 为溶剂， 生成 di(isopropyl)aminodifluorophosphane
  参考文献：
  名称：

  Novel Unique Catalytic Activating Reagents in Synthesis of Biophosphates via the Phosphoramidite Route

  摘要：

  Trimethylchlorosilane (TMSCl) and 2,4-dinitrophenol ore remarkably efficient activators in reaction of P(III) amides with nucleosides to give P(III) esters in excellent yield.

  DOI：

  10.1080/07328319808004696
• 作为产物：
  描述：

  二氯-N,N-二异丙基亚磷酰胺 、 4-nitrophenol sodium salt 以 四氢呋喃 为溶剂， 以95%的产率得到bis(O-4-nitrophenyl)-N,N-diisopropylphosphoramidite
  参考文献：
  名称：

  核苷酸化学中的新型磷酸化试剂，含有两个4-硝基苯氧基离去基团。由DBU激活的显着快速和清洁的磷酸化作用导致硫代和硒代寡核苷酸

  摘要：

  描述了一种新的合成方法，用于修饰基于N，N'-二异丙基-二-（4-硝基苯基）亚磷酰胺1的寡核苷酸。该过程涉及4-硝基苯氧基或二异丙基氨基配体的置换。前者在存在DBU的情况下进展非常快，后者需要被四唑激活。这种方法可以快速，几乎定量地构建衍生自硫代磷酸和硒代磷酸的修饰核苷酸。

  DOI：

  10.1016/0040-4039(93)85068-8

文献信息

• Synthesis of phosphorofluoridates and phosphorofluoridothioates via the phosphoramidite approach
  作者：Wojciech Dabkowski、Izabela Tworowska

  DOI：10.1039/b413552k

  日期：——

  We present a very efficient synthetic procedure leading to the phosphorofluoridates RO-P(O)(OH)F 1 or phosphorofluoridothioates RO-P(S)(OH)F 2, which is based on the intermediary of fluorophosphoramidites (RO)P(F)NiPr25 [R = 9-(hydroxyethyloxymethyl)guaninyl), 3′azido-3′deoxythymidinyl, thymidinyl, anhydrothymidinyl, cholesteryl, N6-benzoyl-5′-O-(4,4′-dimethoxytrityl)-2′-deoxyadenosinyl]. The activation of the amino group was performed with trimethylchlorosilane (TMCS).

  我们介绍了一种非常高效的合成方法，能够制备出磷氟酸盐RO-P(O)(OH)F 1或磷氟硫酸盐RO-P(S)(OH)F 2，其方法基于氟磷酰胺中间体(RO)P(F)NiPr25 [R = 9-(羟乙氧甲基)鸟嘌呤基、3′叠氮-3′脱氧胸苷基、胸苷基、脱水胸苷基、胆固醇基、N6-苯甲酰-5′-O-(4,4′-二甲氧基三苯甲基)-2′-脱氧腺苷基]。氨基的活化采用三甲基氯硅烷（TMCS）完成。
• Novel phosphitylating reagents containing a phosphorus–fluorine bond and their application in efficient synthesis of phosphorofluoridates and phosphorofluoridothionates
  作者：Wojciech Dąbkowski、Izabela Tworowska

  DOI：10.1039/b103082p

  日期：——

  Novel phosphitylating reagents containing a P–F bond are obtained in excellent yield from commercial materials. They react with alcohols at 20 °C in neutral solvents in the presence of tetrazole, chlorotrimethylsilane or benzoyl chloride to give the intermediate phosphorofluoridites. Subsequent oxidation or sulfurization followed by the removal of protecting groups gives the phosphorofluoridates and thiophosphorofluoridates in over 90% total yield.

  包含 P–F 键的新型磷酸化试剂以优异的产率从商业原料中获得。它们在四唑、氯三甲基硅烷或苯甲酰氯的存在下，在中性溶剂中于 20 °C 下与醇反应，生成中间体氟磷酸酯。随后的氧化或硫化处理及保护基团的去除，可得到总产率超过 90% 的氟磷酸酯和硫氟磷酸酯。
• Highly selective O-phosphitylation of amino alcohols using PIIIreagents containing 4-nitro and 2,4-dinitro aryloxy leaving groups
  作者：Wojciech Dabkowski、Alfred Ozarek、Izabela Tworowska

  DOI：10.1039/b509150k

  日期：——

  A method for direct highly O-selective phosphitylation of amino alcohols by reagents containing a 4-nitrophenoxy or 2,4 dinitrophenoxy leaving group has been developed. This method provides mild reaction conditions to access O-phosphitylated amino alcohols. The flexibility of the synthesis is exemplified by the models of simple amino alcohols and of nucleosides containing unprotected NH2 groups.

  开发了一种方法，通过含有4-硝基苯氧基或2,4-二硝基苯氧基离去基团的试剂，实现氨基醇的高度O-选择性膦酸化。这种方法提供了温和的反应条件，用于制备O-膦酸化氨基醇。合成方法的灵活性通过简单氨基醇和含有未保护NH2基团的核苷模型得以展示。
• New Efficient Synthesis of Thymidine Cyclic 3′, 5′- Phosphorofluoridate and Its Sulfur Analogue via the Phosphoroamidite Route
  作者：Wojciech Dąbkowski、Izabela Tworowska、Jan Michalski、Friedrich Cramer

  DOI：10.1080/15257770008045459

  日期：2000.10

  We describe the convenient synthesis of thymidine cyclic 3', 5'-phosphorofluoridate 6, which is superior to that previously reported. Our procedure is based on a sequence of reactions utilizing 3 as the key substrate. Similar sequence of reaction leads to the sulfur analogues of 6 the thymidine cyclic 3',5'-phosphorofluoridothioate 7.

  我们描述了方便的胸腺嘧啶环3'，5'-氟代磷酸酯6的合成，其优于先前报道的。我们的程序基于以3为主要底物的一系列反应。类似的反应顺序产生了胸苷环3'，5'-硫代磷酸氟代酯7的6个硫类似物。
• Model synthesis of 2,3:5,6-di-O-isopropylidene- S-α-D-mannofuranosyl-N,N-diisopropylphosphoramidofluoridothioate and 2,3:5,6-di-O-isopropylidene-Se-α-D-mannofuranosyl-N,N-di-isopropylphosphoramidofluoridoselenoate via P(III)-OAr intermediates and a thiono-thiolo (selenono-selenolo) rearrangement
  作者：Wojciech Dabkowski、Jan Helinski、Lucja Kazimierczak

  DOI：10.3998/ark.5550190.0011.a29

  日期：——

  of the glycosidic center of sugar derivative 2 by phosphoroamidite 1 leads to the intermediate P(III) ester 3. Conversion of 3 into fluorophosphoroamidite 4 and subsequently oxidation by elemental sulfur or selenium affords the corresponding thionoand selenonoesters 5 and 6. The latter compounds are readily rearranged into their thioloor selenoloisomers in the presence of Bu4NI as catalyst (TBAI). The

  糖衍生物 2 的糖苷中心被亚磷酰胺 1 磷酸化得到中间体 P(III) 酯 3。3 转化为氟亚磷酰胺 4，随后被元素硫或硒氧化得到相应的亚硫基和硒基酯 5 和 6。后一种化合物是在作为催化剂 (TBAI) 的 Bu4NI 存在下，它们很容易重排成它们的硫基硒代异构体。7和8的总收率超过90%。