5'-O-(tert-butyldiphenylsilyl)-N⁶-benzoyl-2'-deoxyadenosine | 139244-35-2

• 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: 5'-O-(tert-butyldiphenylsilyl)-N⁶-benzoyl-2'-deoxyadenosine
• 英文别名: 6-N-benzoyl-5'-O-tert-butyldiphenylsilyl-2'-deoxy-N-6-benzoyladenosine；6-N-benzoyl-5'-O-tert-butyldiphenylsilyl-2'-deoxyadenosine；N-[9-[(2R,4S,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-4-hydroxyoxolan-2-yl]purin-6-yl]benzamide
• CAS: 139244-35-2
• 化学式: C₃₃H₃₅N₅O₄Si
• 分子量: 593.758
• InChiKey: LBMIKMOFXXGONY-UPRLRBBYSA-N

物化性质

• 密度：
  1.26±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  43
• 可旋转键数：
  9
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  111
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5'-O-(tert-butyldiphenylsilyl)-N⁶-benzoyl-2'-deoxyadenosine 在 四丁基氟化铵 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 N-苯甲酰基-3’-O-(4,4’-二甲氧基三苯甲基)-2’-脱氧腺苷
  参考文献：
  名称：

  核苷-O-甲基膦酸酯：修饰寡核苷酸的单体池

  摘要：

  四种天然 2'-脱氧核糖核苷、1-（2-脱氧-β-D-苏式-戊呋喃糖基）胸腺嘧啶、5'-O- 和 2' 的一组独特的 5'-O- 和 3'-O-膦酰基甲基衍生物1-(3-脱氧-β-D-赤型-戊呋喃糖基)胸腺嘧啶和1-(3-脱氧-β-D-苏式-戊呋喃糖基)胸腺嘧啶的-O-膦酰基甲基衍生物已被合成为单体库修饰寡核苷酸的合成。膦酸酯部分用 4-甲氧基-1-氧化-2-吡啶基甲酯基团保护，在偶联步骤中也作为分子内催化剂。

  DOI：

  10.1081/ncn-200033912
• 作为产物：
  描述：

  2'-脱氧腺苷 在 氨 作用下， 以 吡啶 、 水 为溶剂， 反应 1.75h， 生成 5'-O-(tert-butyldiphenylsilyl)-N⁶-benzoyl-2'-deoxyadenosine
  参考文献：
  名称：

  Solid-phase synthesis of branched RNA and branched DNA/RNA chimeras

  摘要：

  An effective method for synthesising branched oligonucleotides on solid phase in the 5' to 3' direction has been developed. Special branch-point monomers enable the synthesis of branched oligonucleotides which can have sequences of different length and base composition attached to the 2'-and 3'-hydroxyl groups of the branch point ribonucleoside. The branched oligonucleotides are assembled on commercial DNA synthesisers, the crude products are readily purified by reversed phase HPLC and the fully deprotected products are conveniently analysed by mass spectrometry. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4020(97)00731-x

文献信息

• Efficient Synthesis of 2′-Deoxynucleoside 3′-C-Phosphonates: Reactivity of Geminal Hydroxyphosphonate Moiety
  作者：Śárka Králíková、Miloś Buděšínský、Milena Masojídková、Ivan Rosenberg

  DOI：10.1080/15257770008035038

  日期：2000.7

  In this report we present a novel, simple way for the synthesis of 3'-C-phosphonate derivatives of all four basic 2'-deoxynucleosides in both fully protected and deprotected forms. The reactivity of the geminal hydroxy phosphonate moiety located at the 3'-carbon atom of the nucleoside was studied with respect to the use of this type of nucleoside phosphonic acid for the preparation of short oligonucleotides

  在本报告中，我们提出了一种新颖，简单的方法，用于以完全保护和脱保护的形式合成所有四个基本2'-脱氧核苷的3'-C-膦酸酯衍生物。关于使用这种类型的核苷膦酸制备短寡核苷酸，即二核苷单磷酸类似物，研究了位于核苷的3'-碳原子处的双羟基膦酸酯部分的反应性。
• Synthesis and Properties of ApA Analogues with Shortened Phosphonate Internucleotide Linkage
  作者：Šárka Králíková、Miloš Buděšínský、Ivan Barvík、Milena Masojídková、Zdeněk Točík、Ivan Rosenberg

  DOI：10.1080/15257770.2011.581259

  日期：2011.7

  complete series of the 2 ′–5 ′ and 3 ′–5 ′ regioisomeric types of r(ApA) and 2 ′-d(ApA) analogues with the α-hydroxy-phosphonate C3 ′-O-P-CH(OH)-C4 ″ internucleotide linkage, isopolar but non-isosteric with the phosphodiester one, were synthesized and their hybridization properties with polyU studied. Due to the chirality on the 5 ′-carbon atom of the modified internucleotide linkage bearing phosphorus

  具有α-羟基膦酸酯C3'-OP-CH（OH）-C4的r（ApA）和2'-d（ApA）类似物的2'-5'和3'-5'区域异构体的完整系列合成了与磷酸二酯同等但非等排的核苷酸间键，并研究了它们与polyU的杂交特性。由于具有磷和羟基部分的修饰的核苷酸间键的5'-碳原子上的手性，每个区域异构类型的ApA二聚体被拆分成差向异构对。为了检查α-羟基膦酸酯部分的5'-羟基在杂交过程中的作用，将合适的r（ApA）类似物与3'（2'）-OP-CH 2结合使用合成了缺乏5'-羟基的-C4''键。对修饰的糖-磷酸骨架的构象的核磁共振（NMR）光谱研究以及杂交测量表明，取决于5'-碳原子构型，与polyU的复合物的稳定性存在显着差异。讨论了α-羟基膦酸酯键在修饰的寡核糖核苷酸中的潜在用途。
• Syntheses of Nucleosides Designed for Combinatorial DNA Sequencing
  作者：Mike B. Welch、Carlos I. Martinez、Alex J. Zhang、Song Jin、Richard Gibbs、Kevin Burgess

  DOI：10.1002/(sici)1521-3765(19990301)5:3<951::aid-chem951>3.0.co;2-g

  日期：1999.3.1

  Nucleoside triphosphates I with 3'-O-blocking groups that are both photolabile and fluorescent were required to investigate the viability of a strategy for sequencing DNA in a combinatorial fashion (see Figure 1). Four compounds were prepared to realize this goal. Two of them, 14a and 14t, had dansyl-functionalized, 3'-O-(2"-nitrobenzyl) ether groups, while the other two, 18a and 18t, had similar pendant carbonate groups. Tests for incorporation of these analogues were performed by using five different DNA replicating enzymes, but the analogues were not incorporated. These results were surprising in view of the fact that previous studies had shown that 3'-O-(2"-nitrobenzyl)adenosine triphosphate II was incorporated by Bst DNA polymerase I. However, molecular simulations with the coordinates of a T7 polymerase crystal structure as a model demonstrates that analogues 14a, 14t, 18a and 18t are too large to fit into the enzyme active site, whereas accommodation of the unsubstituted 2-nitrobenzyl compound II is much less demanding. We conclude that both the nucleoside triphosphates and the DNA polymerase enzyme must be modified if the proposed DNA sequencing scheme is to be viable.
• Ribosylation of Pyrimidine 2′-Deoxynucleosides
  作者：Sergey N. Mikhailov、Erik De Clercq、Piet Herdewijn

  DOI：10.1080/07328319608002433

  日期：1996.7

  The previously developed method for the preparation of 2'-O-D-ribofuranosyl-nucleosides is extended to ribosylation of 2'-deoxynucleosides. The scope and limitations of this reaction are discussed.
• Effective Anomerisation of 2′‐Deoxyadenosine Derivatives During Disaccharide Nucleoside Synthesis
  作者：Irina V. Gulyaeva、Kari Neuvonen、Harri Lönnberg、Andrei A. Rodionov、Elena V. Shcheveleva、Georgii V. Bobkov、Ekaterina V. Efimtseva、Sergey N. Mikhailov

  DOI：10.1081/ncn-200040627

  日期：2004.1.12

  The formation of a disaccharide nucleoside (11) by O3'-glycosylation of 5'-O-protected 2'-deoxyadenosine or its N-6-benzoylated derivative has been observed to be accompanied by anomerisation to the corresponding alpha-anomeric product (12). The latter reaction can be explained by instability of the N-glycosidic bond of purine 2'-deoxynucleosides in the presence of Lewis acids. An independent study on the anomerisation of partly blocked 2'-deoxyadenosine has been carried out. Additionally, transglycosylation has been utilized in the synthesis of 3'-O-beta-D-ribofuranosyl-2'deoxyadenosines and its alpha-anomer.