2'-deoxy-2'-C-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-4'-C-vinyluridine | 913972-65-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: 2'-deoxy-2'-C-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-4'-C-vinyluridine
• 英文别名: 1-[(2R,3R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-ethenyl-3-prop-2-enyloxolan-2-yl]pyrimidine-2,4-dione
• CAS: 913972-65-3
• 化学式: C₂₆H₄₆N₂O₅Si₂
• 分子量: 522.833
• InChiKey: JYZQRWHKEZELLQ-INGGGZDUSA-N

物化性质

• 密度：
  1.04±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.59
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  77.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2'-deoxy-2'-C-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-4'-C-vinyluridine 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 四丁基氟化铵 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 30.0h， 生成 (1R,5R,6R,8S)-8-hydroxy-1-hydroxymethyl-6-(uracil-1-yl)-7-oxabicyclo[3.2.1]oct-2-ene
  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：

  (2R,3S,4R,5R)-3-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-5-(2,4-dioxopyrimidin-1-yl)-4-prop-2-enyloxolane-2-carbaldehyde 、 甲基三苯基溴化膦 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.75h， 以95%的产率得到2'-deoxy-2'-C-allyl-3',5'-di-O-(tert-butyldimethylsilyl)-4'-C-vinyluridine
  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

• Synthesis of a bicyclic double-headed nucleoside
  作者：Surender Kumar、Signe Inglev Steffansen、Nanna Albæk、Poul Nielsen

  DOI：10.1016/j.tet.2013.12.013

  日期：2014.1

  with a hemiacetal linker between the C2′ and the C4′-positions was isolated and found to be a suitable substrate for making a conformationally restricted double-headed nucleoside. This contains two uracil nucleobases organized on a bicyclic skeleton and is locked in an N-type conformation.

  使用不同的RCM方法制备碳环LNA模拟的尝试失败。然而，分离出在C2'和C4'-位置之间具有半缩醛连接基的化合物，发现该化合物是制备构象受限的双头核苷的合适底物。它包含组织在双环骨架上的两个尿嘧啶核碱基，并锁定在N型构象中。
• 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.