2'-O-phenoxythiocarbonyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine | 219539-65-8

• 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'-O-phenoxythiocarbonyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine
• CAS: 219539-65-8
• 化学式: C₂₈H₄₄N₂O₇SSi₂
• 分子量: 608.904
• InChiKey: QIBPNOAZKGEGSD-MSNJVRRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  40.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  101.01
• 氢给体数：
  1.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  2'-O-phenoxythiocarbonyl-3',5'-di-O-(tert-butyldimethylsilyl)uridine 在 偶氮二异丁腈 、 溶剂黄146 作用下， 以 甲苯 为溶剂， 反应 75.0h， 生成 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：

  硫代氯甲酸苯酯 、 3',5'-bis-O-(tert-butyldimethylsilyl)uridine 在 4-二甲氨基吡啶 作用下， 以 乙腈 为溶剂， 反应 19.0h， 以79%的产率得到2'-O-phenoxythiocarbonyl-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

• 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.