3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷 | 98495-56-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 中文名称: 3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷
• 英文名称: 3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)-2'-deoxyuridine
• 英文别名: 3',5'-O-(tetraisopropyldisiloxan-1,3-diyl)-2'-deoxyuridine；3',5'-TIPS-2'-Deoxyuridine；1-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]pyrimidine-2,4-dione
• CAS: 98495-56-8
• 化学式: C₂₁H₃₈N₂O₆Si₂
• 分子量: 470.714
• InChiKey: PEDMJTBGYAMVDO-NLWGTHIKSA-N

物化性质

• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.78
• 重原子数：
  31
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  86.3
• 氢给体数：
  1
• 氢受体数：
  6

安全信息

• 储存条件：
  2-8℃

反应信息

• 作为反应物：
  描述：

  3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷 在 K 10 clay 作用下， 以 甲醇 、 水 为溶剂， 反应 60.0h， 以90%的产率得到2-脱氧尿苷
  参考文献：
  名称：

  在甲醇水溶液中用粘土去除乙醛，甲硅烷基和4,4'-二甲氧基三苯甲基保护基与碳水化合物和核苷的羟基官能团。

  摘要：

  DOI：

  10.1021/jo961376r
• 作为产物：
  描述：

  尿嘧啶核苷 在 吡啶 、 4-二甲氨基吡啶 、 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 、 三正丁基氢锡 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 11.0h， 生成 3',5'-O-(1,1,3,3-四异丙基-1,3-DISILOXANEDIYL)-2'-脱氧尿苷
  参考文献：
  名称：

  Smooth and efficient deoxygenation of secondary alcohols. A general procedure for the conversion of ribonucleosides to 2'-deoxynucleosides

  摘要：

  DOI：

  10.1021/ja00394a033

文献信息

• Reactivity of Nucleosides with a Hydroxyl Radical in Non-aqueous Medium
  作者：Gemma M. Rodríguez-Muñiz、M. Luisa Marin、Virginie Lhiaubet-Vallet、Miguel A. Miranda

  DOI：10.1002/chem.201201090

  日期：2012.6.25

  DNA damage: The reactivity of HO. with silylated 2′‐deoxyribonucleosides was investigated in acetonitrile by means of a time‐resolved technique. The obtained rate constants were in general slightly lower than those reported for the natural nucleosides in water. Analysis of the reaction mixture by UPLC‐MS revealed that HO. attack occurred at the nucleobase (see scheme).

  DNA损伤：HO的反应性。通过时间分辨技术研究了乙腈中甲硅烷基化的2'-脱氧核糖核苷的含量。所获得的速率常数通常略低于在水中报道的天然核苷的速率常数。通过UPLC-MS分析反应混合物，发现HO 。攻击发生在核碱基上（见方案）。
• Radical-based deoxygenation of aliphatic alcohols via thioxocarbamate derivatives
  作者：Makoto Oba、Kozaburo Nishiyama

  DOI：10.1016/s0040-4020(01)81751-8

  日期：1994.8

  N-Phenylthioxocarbamates, obtained from the reaction of alcohols with phenyl isothiocyanate in the presence of NaH, were reduced with various silanes such as triethylsilane, triphenylsilane, and tris(trimethylsilyl)silane, as well as tributylstannane under radical conditions to give deoxygenated products of the corresponding alcohols in excellent yields. The reaction was applicable to not only simple aliphatic

  在NaH存在下，将醇与异硫氰酸苯酯反应制得的N-苯基硫代氨基甲酸酯，在自由基条件下，用各种硅烷（如三乙基硅烷，三苯基硅烷和三（三甲基甲硅烷基）硅烷）和三丁基锡烷还原，得到苯甲酸酯的脱氧产物。相应的醇，收率很高。该反应不仅适用于简单的脂族醇，而且适用于糖和核苷。在相似条件下，还研究了使用氘代硅烷和氘代锡烷烷的区域选择性和立体选择性氘代。
• 2′-Deoxyriboguanylurea, the primary breakdown product of 5-aza-2′-deoxyribocytidine, is a mutagen, an epimutagen, an inhibitor of DNA methyltransferases and an inducer of 5-azacytidine-type fragile sites
  作者：Katarzyna Lamparska、Jarrod Clark、Gail Babilonia、Victoria Bedell、Wesley Yip、Steven S. Smith

  DOI：10.1093/nar/gks706

  日期：2012.10

  5-Aza-2′-deoxycytidine (5azaC-dR) has been employed as an inhibitor of DNA methylation, a chemotherapeutic agent, a clastogen, a mutagen, an inducer of fragile sites and a carcinogen. However, its effects are difficult to quantify because it rapidly breaks down in aqueous solution to the stable compound 2′-deoxyriboguanylurea (GuaUre-dR). Here, we used a phosphoramidite that permits the introduction of GuaUre-dR at defined positions in synthetic oligodeoxynucleotides to demonstrate that it is a potent inhibitor of human DNA methyltransferase 1 (hDNMT1) and the bacterial DNA methyltransferase (M. Eco RII) and that it is a mutagen that can form productive base pairs with either Guanine or Cytosine. Pure GuaUre-dR was found to be an effective demethylating agent and was able to induce 5azaC-dR type fragile sites FRA1J and FRA9E in human cells. Moreover, we report that demethylation associated with C:G → G:C transversion and C:G → T:A transition mutations was observed in human cells exposed to pure GuaUre-dR. The data suggest that most of the effects attributed to 5azaC-dR are exhibited by its stable primary breakdown product.

  5-阿扎-2′-脱氧胞苷（5azaC-dR）被用作DNA甲基化的抑制剂、化疗药物、致裂剂、诱变剂、脆弱位点的诱导剂和致癌物。然而，由于其在水溶液中迅速分解为稳定的化合物2′-脱氧核糖鸟苷脲（GuaUre-dR），因此其效应难以量化。在这里，我们使用了一种磷酰胺，使得可以在合成寡脱氧核苷酸中特定位置引入GuaUre-dR，以证明其是人类DNA甲基转移酶1（hDNMT1）和细菌DNA甲基转移酶（M. Eco RII）的强效抑制剂，并且它是一种诱变剂，可以与鸟嘌呤或胞嘧啶形成有效的碱基对。纯GuaUre-dR被发现是一种有效的去甲基化剂，能够在人体细胞中诱导5azaC-dR类型的脆弱位点FRA1J和FRA9E。此外，我们报告在暴露于纯GuaUre-dR的人类细胞中观察到与C:G → G:C反转和C:G → T:A转移突变相关的去甲基化。数据表明，归因于5azaC-dR的大部分效应实际上是其稳定的主要分解产物所体现的。
• Syntheses and Oligonucleotide Incorporation of Nucleoside Analogues Containing Pendant Imidazolyl or Amino Functionalities - The Search for Sequence-Specific Artificial Ribonucleases
  作者：Stephen C. Holmes、Michael J. Gait

  DOI：10.1002/ejoc.200500413

  日期：2005.12

  of six nucleoside phosphoramidite analogues containing pendant protected imidazolyl or amino groups and their incorporation into oligonucleotides. We show that the six functionalised phosphoramidites have similar efficiencies of incorporation and present mass spectral evidence that the composition of an oligonucleotide library of 81 components is consistent with the expected mass mixture distribution

  含有咪唑基和氨基官能团的寡核苷酸衍生物已被提议作为人工核糖核酸酶，可以模拟 RNase A 的活性，但具有更高的序列特异性。这种寡核苷酸试剂作为增强的反义试剂具有重要的应用，无需募集细胞核酸酶或核酸酶复合物。我们展示了六种核苷亚磷酰胺类似物的合成，其中含有侧链保护的咪唑基或氨基，并将它们掺入寡核苷酸中。我们表明，六种功能化亚磷酰胺具有相似的掺入效率，并提供了质谱证据，表明 81 种组分的寡核苷酸库的组成与预期的质量混合物分布一致。因此，此类亚磷酰胺是构建混合寡核苷酸文库的合适起始材料，该文库包含准备用于筛选序列特异性核糖核酸酶活性的咪唑基和氨基修饰的核苷酸区域。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Preparation of Spin-Labeled-2-Amino-dA, dA, dC and 5-Methyl-dC Phosphoramidites for the Automatic Synthesis of EPR Active Oligonucleotides
  作者：Cesare Giordano、Federica Fratini、Donato Attanasio、Luciano Cellai

  DOI：10.1055/s-2001-12355

  日期：——

  2,2,6,6-Tetramethyl-1-piperidinyloxy free radical (TEMPO) labeled phosphoramidites of 2-amino-dA, dA, dC and 5-methyl-dC were synthesized and used for the automatic synthesis of mono-labeled oligodeoxynucleotides (ODNs), which proved active to EPR. It is now possible to insert a paramagnetic probe into nucleic acids in a site- and type-specific manner. The combination of this synthetic approach with EPR spectroscopy can be exploited for performing studies on dynamics and local structural modifications in nucleic acids.

  合成了2,2,6,6-四甲基-1-哌啶氧自由基（TEMPO）标记的2-氨基-dA、dA、dC和5-甲基-dC的磷酰胺类化合物，并用于单标记寡脱氧核苷酸（ODNs）的自动合成，这些化合物对电子顺磁共振（EPR）表现出活性。现在可以以特定的位置和类型将顺磁探针插入核酸中。这种合成方法与EPR光谱的结合可以用于研究核酸中的动态变化和局部结构修饰。