2'-deoxy-2'-allyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine | 219539-68-1

• 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: 2'-deoxy-2'-allyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine
• CAS: 219539-68-1
• 化学式: C₂₄H₄₄N₂O₅Si₂
• 分子量: 496.795
• InChiKey: ZUYKHQFLMLDXJZ-RMVXJAJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  33.0
• 可旋转键数：
  8.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  82.55
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2'-deoxy-2'-allyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine 在 溶剂黄146 作用下， 反应 72.0h， 以75%的产率得到2'-deoxy-2'-C-allyl-3'-O-(tert-butyldimethylsilyl)uridine
  参考文献：
  名称：

  Analogues of a Locked Nucleic Acid with Three-Carbon 2‘,4‘-Linkages:  Synthesis by Ring-Closing Metathesis and Influence on Nucleic Acid Duplex Stability and Structure

  摘要：

  Two bicyclic 2'-deoxynucleoside analogues containing a saturated and an unsaturated three-carbon 2', 4'-linkage, respectively, have been synthesized using a ring-closing metathesis-based linear strategy starting from uridine. Both analogues have been incorporated into oligodeoxynucleotide sequences and increased the stability of DNA:RNA hybrid duplexes (Delta T-m similar to 2.5-5.0 degrees C per modification) and decreased the stability of dsDNA duplexes (Delta T-m similar to 2.5-1.0 degrees C per modification). CD spectroscopy revealed that the bicyclic nucleosides induced formation of A-type-like duplexes albeit to a lesser degree than found for locked nucleic acid (LNA) monomers. From the CD data and UV melting analysis, we propose that the 2'-oxygen atom of the bicyclic moiety is essential for the formation of stabilized A-type-like dsDNA but not for the formation of a stabilized A-type DNA:RNA hybrid.

  DOI：

  10.1021/jo061225g
• 作为产物：
  描述：

  3',5'-bis-O-(tert-butyldimethylsilyl)uridine 在 4-二甲氨基吡啶 、 偶氮二异丁腈 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 22.0h， 生成 2'-deoxy-2'-allyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine
  参考文献：
  名称：

  Analogues of a Locked Nucleic Acid with Three-Carbon 2‘,4‘-Linkages:  Synthesis by Ring-Closing Metathesis and Influence on Nucleic Acid Duplex Stability and Structure

  摘要：

  Two bicyclic 2'-deoxynucleoside analogues containing a saturated and an unsaturated three-carbon 2', 4'-linkage, respectively, have been synthesized using a ring-closing metathesis-based linear strategy starting from uridine. Both analogues have been incorporated into oligodeoxynucleotide sequences and increased the stability of DNA:RNA hybrid duplexes (Delta T-m similar to 2.5-5.0 degrees C per modification) and decreased the stability of dsDNA duplexes (Delta T-m similar to 2.5-1.0 degrees C per modification). CD spectroscopy revealed that the bicyclic nucleosides induced formation of A-type-like duplexes albeit to a lesser degree than found for locked nucleic acid (LNA) monomers. From the CD data and UV melting analysis, we propose that the 2'-oxygen atom of the bicyclic moiety is essential for the formation of stabilized A-type-like dsDNA but not for the formation of a stabilized A-type DNA:RNA hybrid.

  DOI：

  10.1021/jo061225g

文献信息

• A Click Chemistry Approach to Pleuromutilin Derivatives, Part 2: Conjugates with Acyclic Nucleosides and Their Ribosomal Binding and Antibacterial Activity
  作者：Ida Dreier、Surender Kumar、Helle Søndergaard、Maria Louise Rasmussen、Lykke Haastrup Hansen、Nanna Holmgaard List、Jacob Kongsted、Birte Vester、Poul Nielsen

  DOI：10.1021/jm201266b

  日期：2012.3.8

  inhibit protein synthesis. A new series of semisynthetic pleuromutilin derivatives were synthesized by a click chemistry strategy. Pleuromutilin was conjugated by different linkers to a nucleobase, nucleoside, or phenyl group, as a side-chain extension at the C22 position of pleuromutilin. The linkers were designed on the basis of the best linker from our first series of pleuromutilin derivatives following

  截短侧耳素是一种与细菌核糖体结合并因此抑制蛋白质合成的抗生素。通过点击化学策略合成了一系列新的半合成截短侧耳素衍生物。截短侧耳素通过不同的接头缀合至核碱基，核苷或苯基，作为截短侧耳素C22位置的侧链延伸。接头的设计是基于我们第一个截短侧耳素衍生物系列的最佳接头后进行的，即构象限制或等位亚甲基向氧的交换。新化合物与大肠杆菌的结合通过分子建模和核苷酸U2506的化学足迹研究了核糖体，发现所有衍生物都结合到特定位点，并且大多数比截短侧耳素本身更好。还通过核苷酸U2585的化学足迹探索了侧链延伸的作用，结果表明所有化合物都在不同程度上与该位置相互作用。具有接头构象限制的衍生物通常比具有接头中碳原子之一与亲水性氧等位交换的衍生物具有更高的亲和力。用三种不同细菌菌株进行的生长抑制试验显示出几种新化合物的显着活性。
• Two Carbocyclic Locked Nucleic Acid Analogues Give Structural Information about the Role of Hydration in A-Type Duplexes
  作者：Nanna Albæk、Michael Petersen、Poul Nielsen

  DOI：10.1080/15257770701544377

  日期：2007.11.26

  Two locked nucleic acid (LNA) analogues with three-carbon 24 linkages, saturated or unsaturated, are synthesized using a ring-closing metathesis based strategy. Strongly stabilized duplexes with complementary RNA and slightly destabilized duplexes with complementary DNA are observed. CD-spectroscopy indicates a less pronounced shift toward A-type duplexes compared to LNA. These results combining a strong N-type conformation with the absence of a 2'-oxygen demonstrate a stronger importance of minor groove hydration in an intermediate duplex type than in an A-type duplex.