3'-O-(tert-butyldimethylsilyl)-5-iodo-2'-deoxyuridine | 159140-63-3

• 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: 3'-O-(tert-butyldimethylsilyl)-5-iodo-2'-deoxyuridine
• 英文别名: 3'-O-t-butyldimethylsilyl-5-iodo-2'-deoxyuridine；3'-O-[tert-Butyl(dimethyl)silyl]-2'-deoxy-5-iodouridine；1-[(2R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-(hydroxymethyl)oxolan-2-yl]-5-iodopyrimidine-2,4-dione
• CAS: 159140-63-3
• 化学式: C₁₅H₂₅IN₂O₅Si
• 分子量: 468.364
• InChiKey: KGWJPXAJISYTBT-QJPTWQEYSA-N

物化性质

• 熔点：
  187-188 °C
• 密度：
  1.52±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.81
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  88.1
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3'-O-(tert-butyldimethylsilyl)-5-iodo-2'-deoxyuridine 在 四丁基氟化铵 、 sodium hydride 作用下， 以 四氢呋喃 、 二氯甲烷 、 mineral oil 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  IMMUNOMODULATING POLYNUCLEOTIDES, ANTIBODY CONJUGATES THEREOF, AND METHODS OF THEIR USE

  摘要：

  免疫调节多核苷酸被披露。这些免疫调节多核苷酸可能包含5-修饰尿苷、5-修饰胞苷、总共6到16个核苷酸，和/或一个或多个缺失间隔子和/或核苷酸间磷三酯。还披露了含有靶向基团和一个或多个免疫调节多核苷酸的结合物。这些免疫调节多核苷酸和结合物可能进一步包含一个或多个辅助基团。还披露了含有这些免疫调节多核苷酸或含有一个或多个立体化富集的核苷酸间磷硫酸酯的结合物的组合物。进一步披露了含有这些免疫调节多核苷酸或结合物的药物组合物以及它们的使用方法。

  公开号：

  US20180312536A1
• 作为产物：
  描述：

  碘苷 在 咪唑 、 溶剂黄146 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 76.0h， 生成 3'-O-(tert-butyldimethylsilyl)-5-iodo-2'-deoxyuridine
  参考文献：
  名称：

  Synthesis and Spectroscopic Properties of Porphyrin-Substituted Uridine and Deoxyuridine

  摘要：

  本文介绍了利用乙炔卟啉的 Sonogashira 偶联合成卟啉取代的尿苷和 2′-脱氧尿苷的一般合成路线。二苯卟啉和四苯卟啉，无论是游离基还是金属锌，都可以连接到核碱基上。脱氧核糖的选择性 TBDMS 保护不会影响偶联反应。卟啉上的取代基使轭合物可溶于有机溶剂（羧酸酯）或水（羧酸盐）。紫外/可见光谱显示，发色团与核碱基之间不会发生电子通讯。在水溶液中，卟啉的吸收率大大低于在有机溶剂中的吸收率。

  DOI：

  10.1055/s-2004-829541

文献信息

• A Practical Method for Regioselective 5′-O-tert-Butyldimethylsilyl Deprotection of Persilylated Nucleosides by Methanolic Phosphomolybdic Acid
  作者：Shan-Shan Gong、Qi Sun、Hua-Shan Huang、Rui Kong、Xiu-An Zheng、Wei-Jie Chen、Shuai-Bo Han、De-Yun Zeng

  DOI：10.1055/s-0037-1610300

  日期：2018.11

  In nucleoside/nucleotide chemistry, the regioselective cleavage of 5′-O-TBS groups of persilylated nucleosides is a desired approach for structural functionalization at the 5′-position. However, efficient and practical methods for this purpose are still limited. In our research, we found that homogeneous methanolic phosphomolybdic acid (PMA) efficiently catalyzes the regioselective deprotection of

  在核苷/核苷酸化学中，全甲硅烷基化核苷的 5'-O-TBS 基团的区域选择性切割是 5' 位结构功能化的理想方法。然而，用于此目的的有效和实用的方法仍然有限。在我们的研究中，我们发现均相甲醇磷钼酸 (PMA) 可有效催化多种全甲硅烷基化核苷底物的 5'-O-TBS 基团的区域选择性脱保护，并可用于实际合成，规模可达 15 g。31P NMR 结果表明形成了阴离子簇，且均相 PMA 的路易斯酸度取决于有机溶剂。甲醇 PMA 的功效和显着的区域选择性是由于磷酸钼阴离子溶剂化后路易斯酸强度降低的结果。
• Synthesis and Conformational Analyses of Cyclonucleoside Having 13-Membered Ring Bridging Nucleobase and 5′-Position via a Linker Containing Sulfonamide
  作者：Takayuki Kanagawa、Shigetoshi Tachibana、Yoshiaki Masaki、Kohji Seio

  DOI：10.1021/acs.orglett.3c03094

  日期：2023.11.3

  intermediate that contained both a sulfonyltriazole and amino groups. Both 1H NMR and computational studies revealed that the sugar conformation, base orientation, and γ torsion angle were S-type, anti, and trans, respectively. As such, cyclic nucleosides show promise for introducing these specific distorted conformations into functional nucleic acids.

  环状核苷已被设计和合成，作为功能性寡核苷酸开发的构象固定构件。在核碱基和 5'-位之间引入桥，以同时固定围绕 C4'-C5' 键的旋转、碱基方向和糖褶皱。使用磺酰胺键引入 13 元环状结构，该键保留可用于连接额外核苷部分的 N-H 基团。磺酰胺键是通过含有磺酰三唑和氨基的中间体的端到端环化形成的。 1 H NMR和计算研究表明糖构象、碱基方向和γ扭转角分别为S型、反式和反式。因此，环状核苷有望将这些特定的扭曲构象引入功能性核酸中。
• Design and Synthesis of 3‘- and 5‘-<i>O</i>-(3-Benzenesulfonylfuroxan-4-yl)-2‘-deoxyuridines:  Biological Evaluation as Hybrid Nitric Oxide Donor−Nucleoside Anticancer Agents
  作者：Sameh Moharram、Aihua Zhou、Leonard I. Wiebe、Edward E. Knaus

  DOI：10.1021/jm030544m

  日期：2004.3.1

  A group of 3'-O- and 5'-O-(3-benzenesulfonylfuroxan-4-yl)-2'-deoxyuridines possessing a variety of substituents (H, Me, 1, F, CF3) at the C-5 position of the nucleoside moiety were synthesized for evaluation as hybrid anticancer agents that have the ability to simultaneously release cytotoxic nitric oxide ((NO)-N-.). Incubation of these nitric oxide donor-nucleoside conjugates in the presence of 18 MM L-cysteine released a high percentage of (NO)-N-. (21-48% at 1 h; 37-86% at 16 h). The release of (NO)-N-. in the absence of the thiol cofactor was negligible. These hybrid (NO)-N-. donor-nucleosides exhibited high cellular toxicity (CC50 = 10(-6)-10(-8) M range) against a battery of tumor cell lines (143B-LTK, 14313, EMT-6, KBALB-STK, and KBALB) and normal human fibroblasts (Hs578Bst). No differences in cytotoxicity between nontransfected (143B, KBALB) and the corresponding transfected (143B-LTK, KBALB-STK) cancer cell lines possessing the herpes simplex virus type 1 (HSV-1) thymidine kinase gene (TK+) were observed, indicating that expression of the viral TK enzyme did not provide a gene therapeutic effect.
• IMMUNOMODULATING POLYNUCLEOTIDES, ANTIBODY CONJUGATES THEREOF, AND METHODS OF THEIR USE
  申请人：SOLSTICE BIOLOGICS, LTD.

  公开号：US20180312536A1

  公开（公告）日：2018-11-01

  Immunomodulating polynucleotides are disclosed. The immunomodulating polynucleotides may contain 5-modified uridine, 5-modified cytidine, a total of from 6 to 16 nucleotides, and/or one or more abasic spacers and/or internucleoside phosphotriesters. Also disclosed are conjugates containing a targeting moiety and one or more immunomodulating polynucleotides. The immunomodulating polynucleotides and conjugates may further contain one or more auxiliary moieties. Also disclosed are compositions containing the immunomodulating polynucleotides or the conjugates containing one or more stereochemically enriched internucleoside phosphorothioates. Further disclosed are pharmaceutical compositions containing the immunomodulating polynucleotides or the conjugates and methods of their use.

  免疫调节多核苷酸被披露。这些免疫调节多核苷酸可能包含5-修饰尿苷、5-修饰胞苷、总共6到16个核苷酸，和/或一个或多个缺失间隔子和/或核苷酸间磷三酯。还披露了含有靶向基团和一个或多个免疫调节多核苷酸的结合物。这些免疫调节多核苷酸和结合物可能进一步包含一个或多个辅助基团。还披露了含有这些免疫调节多核苷酸或含有一个或多个立体化富集的核苷酸间磷硫酸酯的结合物的组合物。进一步披露了含有这些免疫调节多核苷酸或结合物的药物组合物以及它们的使用方法。
• Synthesis and Spectroscopic Properties of Porphyrin-Substituted Uridine and Deoxyuridine
  作者：Eugen Stulz、Imenne Bouamaied

  DOI：10.1055/s-2004-829541

  日期：——

  A general synthetic route to porphyrin-substituted uridine and 2′-deoxyuridine using Sonogashira coupling with acetylene porphyrins is presented. Both diphenyl and tetraphenyl porphyrins, as free base or zinc metallated, can be attached to the nucleobase. Selective TBDMS protection of the deoxyribose does not affect the coupling reaction. The substituents on the porphyrins render the conjugates soluble either in organic solvents (carboxy ­esters) or in water (carboxylates). No electronic communication ­between the chromophore and the nucleobase occurs, as indicated by UV/Vis spectroscopy. In aqueous solution, the absorption of the porphyrins is substantially lower than in organic solvents.

  本文介绍了利用乙炔卟啉的 Sonogashira 偶联合成卟啉取代的尿苷和 2′-脱氧尿苷的一般合成路线。二苯卟啉和四苯卟啉，无论是游离基还是金属锌，都可以连接到核碱基上。脱氧核糖的选择性 TBDMS 保护不会影响偶联反应。卟啉上的取代基使轭合物可溶于有机溶剂（羧酸酯）或水（羧酸盐）。紫外/可见光谱显示，发色团与核碱基之间不会发生电子通讯。在水溶液中，卟啉的吸收率大大低于在有机溶剂中的吸收率。