5'-O-(4,4'-dimethoxytrityl)-2'-O-(tert-butyldimethylsilyl)uridin-3'-yl H-phosphonate | 117363-66-3

• 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: 5'-O-(4,4'-dimethoxytrityl)-2'-O-(tert-butyldimethylsilyl)uridin-3'-yl H-phosphonate
• 英文别名: 5'-O-DMTr-2'-O-tBDMS-uridine 3'-H-phosphonate；5'-O-dimethoxytrityl-2'-O-tert-butyldimethylsilyl-uridin-3'-yl H-phosphonate；[(2R,3R,4R,5R)-2-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[tert-butyl(dimethyl)silyl]oxy-5-(2,4-dioxopyrimidin-1-yl)oxolan-3-yl]oxyphosphinic acid
• CAS: 117363-66-3
• 化学式: C₃₆H₄₅N₂O₁₀PSi
• 分子量: 724.82
• InChiKey: GDYRQHIHSODBBA-WXQJYUTRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.62
• 重原子数：
  50.0
• 可旋转键数：
  13.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  147.54
• 氢给体数：
  2.0
• 氢受体数：
  10.0

反应信息

• 作为反应物：
  描述：

  5'-O-(4,4'-dimethoxytrityl)-2'-O-(tert-butyldimethylsilyl)uridin-3'-yl H-phosphonate 在 二氯乙酸 、 ammonium hydroxide 、 三乙胺-硼烷 、 四丁基氟化铵 、 三甲基乙酰氯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 生成 diuridine 3',5'-boranophosphate
  参考文献：
  名称：

  Synthesis of diuridine 3′,5′-boranophosphate: H-phosphonate approach

  摘要：

  Diuridine 3',5'-boranophosphate, the RNA analogue of boranophosphate nucleic acids, was synthesized by a new approach via the H-phosphonate. Two diastereomers of diuridine 3',5'-boranophosphate were separated by reverse phase HPLC. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00742-x
• 作为产物：
  描述：

  在 叔丁胺 作用下， 以 乙腈 为溶剂， 反应 0.17h， 生成 5'-O-(4,4'-dimethoxytrityl)-2'-O-(tert-butyldimethylsilyl)uridin-3'-yl H-phosphonate
  参考文献：
  名称：

  Synthesis of All Possible Canonical (3′–5′-Linked) Cyclic Dinucleotides and Evaluation of Riboswitch Interactions and Immune-Stimulatory Effects

  摘要：

  The cyclic dinucleotides (CDNs) c-di-GMP, c-di-AMP, and c-AMP-GMP are widely utilized as second messengers in bacteria, where they signal lifestyle changes such as motility and biofilm formation, cell wall and membrane homeostasis, virulence, and exo-electrogenesis. For all known bacterial CDNs, specific riboswitches have been identified that alter gene expression in response to the second messengers. In addition, bacterial CDNs trigger potent immune responses, making them attractive as adjuvants in immune therapies. Besides the three naturally occurring CDNs, seven further CDNs containing canonical 3'-5'-linkages are possible by combining the four natural ribonucleotides. Herein, we have synthesized all ten possible combinations of 3'-5'-linked CDNs. The binding affinity of novel CDNs and GEMM riboswitch variants was assessed utilizing a spinach aptamer fluorescence assay and in-line probing assays. The immune-stimulatory effect of CDNs was evaluated by induction of type I interferons (IFNs), and a novel CDN c-AMP-CMP was identified as a new immune-stimulatory agent.

  DOI：

  10.1021/jacs.7b06141

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。
• Stereochemistry of internucleotide bond formation by the H-phosphonate method. Part 3: Investigations on a mechanism of asymmetric induction
  作者：Michal Sobkowski、Adam Kraszewski、Jacek Stawinski

  DOI：10.1016/j.tetasy.2007.09.017

  日期：2007.9

  The stereochemistry of H-phosphonate diester bond formation (including internucleotide ones) with ribonucleoside H-phosphonates as substrates has been investigated using 31P NMR spectroscopy. It was found that the reactions investigated owe their stereoselectivity to a dynamic kinetic asymmetric transformation. The absolute configurations of the compounds involved in the reaction pathways were tentatively

  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。
• 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.
• ARYL NUCLEOSIDE H-PHOSPHONATES AS A TOOL FOR INVESTIGATION OF STEREOSPECIFICITY DURING COUPLING
  作者：Michal Sobkowski、Jadwiga Jankowska、Jacek Stawinski、Adam Kraszewski

  DOI：10.1081/ncn-200059239

  日期：2005.4.1

  It was found that in stereoselective condensations of ribonucleoside 3'-H-phosphonates with alcohols, the major diastereomer of the produced H-phosphonate diesters is formed from the minor diastereomer of the intermediate phosphonic-pivalic anhydride.