N4-benzoyl-O3',O5'-bis(tert-butyldimethylsilyl)-2'-deoxycytidine | 51549-38-3

• 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: N4-benzoyl-O3',O5'-bis(tert-butyldimethylsilyl)-2'-deoxycytidine
• 英文别名: N⁴-benzoyl-O^3',O^5'-bis(tert-butyldimethylsilyl)-2'-deoxycytidine；N⁴-benzoyl-3',5'-bis-O-(tert-butyldimethylsilyl)-2'-deoxycytidine；4-N-benzoyl-2'-deoxy-3',5'-bis-O-(tert-butyldimethylsilyl)cytidine；N⁴-benzoyl-O^3'_,O5'-bis-(tert-butyl-dimethyl-silanyl)-2'-deoxy-cytidine
• CAS: 51549-38-3
• 化学式: C₂₈H₄₅N₃O₅Si₂
• 分子量: 559.853
• InChiKey: ORMGQMZXCGUALD-WMTXJRDZSA-N

物化性质

• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  38.0
• 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：
  91.68
• 氢给体数：
  1.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  N4-benzoyl-O3',O5'-bis(tert-butyldimethylsilyl)-2'-deoxycytidine 在 ammonium hydroxide 作用下， 以 水 为溶剂， 反应 0.33h， 生成 N-苯甲酰-2'-脱氧胞苷
  参考文献：
  名称：

  Unexpected Shift to a 4-Imino Tautomer Upon N⁴-Acylation of 5-Methylcytosin-1-yl Nucleoside Analogues

  摘要：

  In contrast with the behaviour of 5-unsubstituted cytosine nucleoside analogues, 5-methylcytosine derivatives show upon N-4-benzoylation, commonly used as base protection in oligonucleotide synthesis, a tautomeric change of the base moiety from a 4-amino- into a 4-imino isomer. In the latter form, which is easily diagnosticized by C-13 NMR and confirmed by X-ray data, the compounds seem to be hydrolytically less stable.

  DOI：

  10.1080/15257779908041652
• 作为产物：
  描述：

  2'-脱氧胞嘧啶核苷 以 吡啶 为溶剂， 反应 2.0h， 生成 N4-benzoyl-O3',O5'-bis(tert-butyldimethylsilyl)-2'-deoxycytidine
  参考文献：
  名称：

  Unexpected Shift to a 4-Imino Tautomer Upon N⁴-Acylation of 5-Methylcytosin-1-yl Nucleoside Analogues

  摘要：

  In contrast with the behaviour of 5-unsubstituted cytosine nucleoside analogues, 5-methylcytosine derivatives show upon N-4-benzoylation, commonly used as base protection in oligonucleotide synthesis, a tautomeric change of the base moiety from a 4-amino- into a 4-imino isomer. In the latter form, which is easily diagnosticized by C-13 NMR and confirmed by X-ray data, the compounds seem to be hydrolytically less stable.

  DOI：

  10.1080/15257779908041652

文献信息

• A Practical Method for Regioselective 5′-O-tert-Butyldimethylsilyl Deprotection of Persilylated Nucleosides by Methanolic Phosphomolybdic Acid
  作者：Shan-Shan Gong、Qi Sun、Hua-Shan Huang、Rui Kong、Xiu-An Zheng、Wei-Jie Chen、Shuai-Bo Han、De-Yun Zeng

  DOI：10.1055/s-0037-1610300

  日期：2018.11

  In nucleoside/nucleotide chemistry, the regioselective cleavage of 5′-O-TBS groups of persilylated nucleosides is a desired approach for structural functionalization at the 5′-position. However, efficient and practical methods for this purpose are still limited. In our research, we found that homogeneous methanolic phosphomolybdic acid (PMA) efficiently catalyzes the regioselective deprotection of

  在核苷/核苷酸化学中，全甲硅烷基化核苷的 5'-O-TBS 基团的区域选择性切割是 5' 位结构功能化的理想方法。然而，用于此目的的有效和实用的方法仍然有限。在我们的研究中，我们发现均相甲醇磷钼酸 (PMA) 可有效催化多种全甲硅烷基化核苷底物的 5'-O-TBS 基团的区域选择性脱保护，并可用于实际合成，规模可达 15 g。31P NMR 结果表明形成了阴离子簇，且均相 PMA 的路易斯酸度取决于有机溶剂。甲醇 PMA 的功效和显着的区域选择性是由于磷酸钼阴离子溶剂化后路易斯酸强度降低的结果。
• 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.
• Rapid syntheses of protected 2'-deoxycytidine derivatives
  作者：Jean Igolen、Christophe Morin

  DOI：10.1021/jo01311a061

  日期：1980.11
• Structure−Function Studies on a Synthetic Guanosine Receptor That Simultaneously Binds Watson−Crick and Hoogsteen Sites
  作者：Jordan R. Quinn、Steven C. Zimmerman

  DOI：10.1021/jo0501689

  日期：2005.9.1

  A series of receptors (11-16) designed to simultaneously bind the Watson-Crick and Hoogsteen sites of guanosine were synthesized, and their binding of guanosine tri-O-pentanoate (32) was probed via H-1 NMR complexation studies in 5% DMSO-d(6)-chloroform-d. The guanosine receptors were synthesized with aminonaphthalene or aminoquinoline auxiliary groups tethered to N-4 of cytosine via a methylene or carbonyl group. A structure -function relationship was established allowing energetic contributions made by components of nucleoside analogues to be probed and more general design rules formulated that may guide the development of more efficacious DNA bases.