1-[(2R,3R,4R,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-[ethoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]pyrimidine-2,4-dione | 1242653-00-4

• 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: 1-[(2R,3R,4R,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-[ethoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]pyrimidine-2,4-dione
• CAS: 1242653-00-4
• 化学式: C₃₈H₄₉N₂O₁₀PSi
• 分子量: 752.874
• InChiKey: UTRPDYUZNSOKCI-HYGOWAQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  52
• 可旋转键数：
  16
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  137
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  1-[(2R,3R,4R,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-[ethoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]pyrimidine-2,4-dione 在 sulfur 作用下， 生成 、
  参考文献：
  名称：

  通过H-膦酸酯方法形成核苷酸间键的立体化学。7.立体选择性形成核糖核苷（R P）-和（S P）-3'- H-硫代磷酸单酯

  摘要：

  核糖核苷3'- H-硫代磷酸单酯以（R P）-和（S P）-非对映异构体形式存在。为了以高收率和高立体化学纯度获得它们，研究了其制备的立体选择策略。为了合成（R P）-异构体，开发了活化核苷H-膦酸酯的立体选择性硫水解，同时通过不对称转化核苷3'- H的非对映异构体混合物制备了具有（S P）-构型的单酯。-硫代磷酸酯，可使用与9-芴甲醇的缩合反应，然后进行β-消除，或通过Pivaloylation-hydrolysis反应顺序进行。通过立体化学相关分析，初步确定了所获得的3'- H-硫代磷酸膦酸酯的非对映异构体的绝对构型。

  DOI：

  10.1016/j.tetasy.2010.01.022
• 作为产物：
  描述：

  5'-O-(4,4'-dimethoxytrityl)-2'-O-(tert-butyldimethylsilyl)uridin-3'-yl H-phosphonate 在 2,6-二甲基吡啶 、 三甲基乙酰氯 作用下， 以 二氯甲烷 为溶剂， 生成 1-[(2R,3R,4R,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-3-[tert-butyl(dimethyl)silyl]oxy-4-[ethoxy(oxido)phosphaniumyl]oxyoxolan-2-yl]pyrimidine-2,4-dione
  参考文献：
  名称：

  通过H-膦酸酯方法形成核苷酸间键的立体化学。第3部分：不对称感应机制的研究

  摘要：

  使用31 P NMR光谱研究了以核糖核苷H-膦酸酯为底物的H-膦酸酯二酯键形成（包括核苷酸间键）的立体化学。发现所研究的反应归因于它们的立体选择性，这归因于动态动力学不对称转化。根据它们的31 P NMR化学位移，初步确定了参与反应路径的化合物的绝对构型，并验证了H-膦酸酯-新戊酸酯混合酸酐和H-膦酸酯芳基酯的正确性。

  DOI：

  10.1016/j.tetasy.2007.09.017

文献信息

• Stereochemistry of Internucleotide Bond Formation by the H-Phosphonate Method. 1. Synthesis and ³¹P Nmr Analysis of 16 Diribonulceoside (3′-5′)-H-Phosphonates and the Corresponding Phosphorothioates
  作者：Michal Sobkowski、Jadwiga Jankowska、Adam Kraszewski、Jacek Stawinski

  DOI：10.1080/15257770500265729

  日期：2005.9.1

  Sixteen diribonucleoside (3′-5′)-H-phosphonates were synthesized via condensation of the protected ribonucleoside 3′-H-phosphonates with nucleosides, and the influence of a nucleoside sequence on the observed stereoselectivity was analyzed. 31P NMR spectroscopy was used to evaluate a relationship between chemical shift and absolute configuration at the phosphorous center of the H-phosphonate diesters

  通过受保护的核糖核苷 3'-H-膦酸酯与核苷的缩合合成了 16 种二核糖核苷 (3'-5')-H-膦酸酯，并分析了核苷序列对观察到的立体选择性的影响。31P NMR光谱用于评估H-膦酸二酯以及相应硫代磷酸二酯的磷中心的化学位移和绝对构型之间的关系。尽管在大多数情况下发现了这种相关性，但也有一些例外，即由 RP 和 SP 非对映异构体产生的共振的相对位置颠倒的规则。
• Synthesis of Pyridiniumboranephosphonate Diesters and Related Compounds using Trityl Cation as a Borane Hydride Acceptor
  作者：Jacek Stawinski、Marta Rachwalak、Justyna Gołębiewska、Tomasz Jakubowski

  DOI：10.1055/s-0040-1706569

  日期：2021.2

  Boranephosphonate diesters react with pyridine and some tertiary amines in the presence of dimethoxytrityl chloride used as a borane­ hydride acceptor, to afford the boron-modified phosphodiester analogues containing a P-B-N structural motif. The reaction provides a convenient entry to pyridinium- and ammoniumboranephosphonates derived from the corresponding alkyl, aryl, or nucleoside boranephosphonate

  在用作甲硼烷氢化物受体的二甲氧基三苯甲基氯的存在下，硼烷膦酸酯二酯与吡啶和一些叔胺反应，得到含有PBN结构基序的硼改性的磷酸二酯类似物。该反应为衍生自相应的烷基，芳基或核苷硼烷膦酸酯二酯的吡啶鎓-硼烷膦酸铵和铵盐提供了便利的入口。讨论了合成方案的某些方面，与可能的中间体有关的机械特性以及所用溶剂的作用。
• The role of nucleophilic catalysis in chemistry and stereochemistry of ribonucleosideH-phosphonate condensation
  作者：Michal Sobkowski、Jacek Stawinski、Adam Kraszewski

  DOI：10.1039/b812780h

  日期：——

  The efficiency and stereoselectivity of condensation of ribonucleoside 3′-H-phosphonates with alcohols were investigated as a function of amines used for the reaction. It was found that irrespective of the presence or absence of nucleophilic catalysts, the Dynamic Kinetic Asymmetric Transformation (DYKAT) was the major factor responsible for the stereoselective formation of the DP(SP) isomers of the H-phosphonate diesters, and a mechanistic rationalization of this observation was proposed. In addition, studies on the reactions carried out in the presence of various bases led to the conclusion that certain sterically hindered pyridines, e.g.2,6-lutidine, may act as nucleophilic catalysts in the condensation of ribonucleoside 3′-H-phosphonates with alcohols.

  研究了核糖核苷3′-H-磷酸酯与醇的缩合反应的效率和立体选择性，作为反应中使用的胺的函数。结果发现，无论是否存在亲核催化剂，动态动力学不对称转化（DYKAT）是导致H-磷酸二酯DP(SP)异构体立体选择性形成的主要因素，并提出了对此观察结果的机制解释。此外，对在各种碱存在下进行的反应的研究得出结论，某些空间位阻较大的吡啶类化合物，例如2,6-路丁啶，可能在核糖核苷3′-H-磷酸酯与醇的缩合反应中起到亲核催化剂的作用。
• Stereochemistry of Internucleotide Bond Formation by the<i>H-</i>Phosphonate Method. 5. The Role of Brønsted and H-Bonding Base Catalysis in Ribonucleoside<i>H-</i>Phosphonate Condensation—Chemical and Stereochemical Consequences
  作者：Michal Sobkowski、Jacek Stawinski、Adam Kraszewski

  DOI：10.1080/15257770.2010.497014

  日期：2010.7.20

  were assessed. Several tertiary amines promoted condensations with stereoselectivity higher than that observed for pyridine derivatives. A correlation between diastereoselectivity of the product formation and Brønsted and H-bonding basicities of the amine used was found.

  研究了新戊酰氯促进的核糖核苷3'- H-膦酸酯与乙醇缩合的效率和立体选择性与所用叔胺的关系。确认导致对缩合剂需求增加的副反应是由于新戊酸酯在反应性新戊酰基衍生物的羰基中心处的进攻而引起的。评估确保定量获得H-膦酸酯二酯缩合的条件。几种叔胺促进的缩合反应的立体选择性高于吡啶衍生物。发现产物形成的非对映选择性与所用胺的布朗斯台德和H键碱性之间的相关性。
• Stereochemistry of internucleotide bond formation by the H-phosphonate method. Part 6: Optimization of the reaction conditions towards highest stereoselectivity
  作者：Michal Sobkowski、Jacek Stawinski、Adam Kraszewski

  DOI：10.1016/j.tetasy.2008.11.002

  日期：2008.11

  The condensations of ribonucleoside 3'-H-phosphonates with simple alcohols and nucleosides are known to be stereoselective reactions that favour formation of D-P(S-P)-diastereomers of the produced H-phosphonate diesters without engaging any chiral auxiliaries. We have investigated various reaction conditions in order to attain the highest stereoselectivity for the condensation. With an optimal choice of solvents, reagent concentrations, temperature and the condensing agent used, the diastereomeric excess of the D-P(S-P)-isomers of dinucleoside H-phosphonates was enhanced from the initial 50-70% to ca. 85%. (C) 2008 Elsevier Ltd. All rights reserved.