N⁶-benzoyl-O^3'_,O5'-bis-(tert-butyl-dimethyl-silanyl)-2'-deoxy-adenosine | 51549-41-8

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘌呤核苷
• 英文名称: N⁶-benzoyl-O^3'_,O5'-bis-(tert-butyl-dimethyl-silanyl)-2'-deoxy-adenosine
• 英文别名: N-[9-[(2R,4S,5R)-4-[tert-butyl(dimethyl)silyl]oxy-5-[[tert-butyl(dimethyl)silyl]oxymethyl]oxolan-2-yl]purin-6-yl]benzamide
• CAS: 51549-41-8
• 化学式: C₂₉H₄₅N₅O₄Si₂
• 分子量: 583.878
• InChiKey: VSGHXYQIYNAXGQ-YTFSRNRJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.78
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  100
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  N⁶-benzoyl-O^3'_,O5'-bis-(tert-butyl-dimethyl-silanyl)-2'-deoxy-adenosine 在 三氟乙酸 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以73%的产率得到N-苯甲酰-2'-脱氧-3'-O-(1,1-二甲基乙基)二甲基硅氧基-腺苷
  参考文献：
  名称：

  Facile and highly selective 5′-desilylation of multisilylated nucleosides

  摘要：

  介绍了选择性地对多硅烷基化核苷进行 5'-去硅烷基化的高效方法。

  DOI：

  10.1039/b003562i
• 作为产物：
  描述：

  8-溴-2'-脱氧腺苷 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 air 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 作用下， 以 氟苯 、 N,N-二甲基甲酰胺 为溶剂， 反应 5.0h， 生成 N⁶-benzoyl-O^3'_,O5'-bis-(tert-butyl-dimethyl-silanyl)-2'-deoxy-adenosine
  参考文献：
  名称：

  C5‘-Adenosinyl Radical Cyclization. A Stereochemical Investigation

  摘要：

  A variety of substituted 2'-deoxyadenosin-5'-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5'S,8R)-4 and (5'R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5'-radical cyclization have been considered. The observed increase of the (5'S)/(5'R) ratio by increasing the bulkiness of the R-1 group is explained in terms of steric repulsion between R-1 and the purine moiety which favors the C5'-endo conformation, whereas the effect of the water solvent in promoting the (5'R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5'-exo confomation.

  DOI：

  10.1021/jo060197z

文献信息

• Synthesis and Properties of DNA Oligomers Containing 2‘-Deoxynucleoside <i>N</i>-Oxide Derivatives
  作者：Hirosuke Tsunoda、Akihiro Ohkubo、Haruhiko Taguchi、Kohji Seio、Mitsuo Sekine

  DOI：10.1021/jo7021845

  日期：2008.2.1

  reported about the chemical and biochemical behavior of initially formed DNA oligomers containing these N-oxide bases. In this study, we established a convenient method for the solid-phase synthesis of oligodeoxynucleotides incorporating 2‘-deoxycytidine N-oxide (dCO) or 2‘-deoxyadenosine N-oxide (dAO) by using the postsynthetic oxidation of N-protected DNA oligomers except for the target dC or dA site

  长期以来，人们一直认为胞嘧啶和腺嘌呤N-氧化物衍生物是由过氧化物（例如过氧化氢）对DNA的氧化破坏而产生的产物。尽管已经很好地描述了2'-脱氧核苷N-氧化物衍生物的合成和性质，但是关于最初形成的包含这些N-氧化物碱基的DNA低聚物的化学和生物化学行为的报道很少。在这项研究中，我们建立了一种方便的固相合成寡脱氧核苷酸的方法，其中包含2'-脱氧胞苷N-氧化物（dC O）或2'-脱氧腺苷N-氧化物（dA O），使用m- CPBA在MeOH中以高度选择性的方式使用N-保护的DNA低聚物（目标dC或dA位点除外）进行后合成氧化。在该策略中，苯甲酰基，邻苯二甲酰基和（4-异丙基苯氧基）乙酰基被证明可作为碱基保护基团，以避免未修饰位点分别氧化腺嘌呤，胞嘧啶和鸟嘌呤。
• TRANSPROTECTION OF SILYL ETHERS OF NUCLEOSIDES IN FeCl₃ BASED IONIC LIQUIDS
  作者：Jitendra R. Harjani、Susheel J. Nara、Manikrao M. Salunkhe、Yogesh S. Sanghvi

  DOI：10.1081/ncn-200060305

  日期：2005.4.1

  Ionic liquid mediated deprotection of tert-butyldimethyl silyl (TBDMS) ethers derived from various primary and secondary alcohols have been studied and the reaction conditions optimized Deprotection of the silyl ethers in FeCl3 based ionic liquids in presence of acetic anhydride yielded the acetate esters of the corresponding alcohols in good yields. The transprotection methodology was extended to the silyl ethers Of nucleosides to yield the corresponding acetylated products.
• Facile and highly selective 5′-desilylation of multisilylated nucleosides
  作者：Xue-Feng Zhu、Howard J. Williams、A. Ian Scott

  DOI：10.1039/b003562i

  日期：——

  Efficient methods for selective 5'-desilylation of multisilylated nucleosides are described.

  介绍了选择性地对多硅烷基化核苷进行 5'-去硅烷基化的高效方法。
• C5‘-Adenosinyl Radical Cyclization. A Stereochemical Investigation
  作者：Maria Luisa Navacchia、Chryssostomos Chatgilialoglu、Pier Carlo Montevecchi

  DOI：10.1021/jo060197z

  日期：2006.6.1

  A variety of substituted 2'-deoxyadenosin-5'-yl radicals 3 were generated under different reaction conditions. Radicals 3 underwent intramolecular cyclization onto the C8-N7 double bond of the adenine moiety leading to aminyl radicals (5'S,8R)-4 and (5'R,8R)-4 and, eventually, to the corresponding cyclonucleosides 5 and 6. The effect of the solvent, the nature of the substituents, and the generation method of radicals 3 on the stereoselectivity of the C5'-radical cyclization have been considered. The observed increase of the (5'S)/(5'R) ratio by increasing the bulkiness of the R-1 group is explained in terms of steric repulsion between R-1 and the purine moiety which favors the C5'-endo conformation, whereas the effect of the water solvent in promoting the (5'R)-stereoselective cyclization is ascribed to intermolecular hydrogen bonding stabilizing the C5'-exo confomation.