2'-deoxy-2'-α-C-(2-hydroxyethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine | 171503-88-1

• 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'-α-C-(2-hydroxyethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine
• 英文别名: 2'-deoxy-2'-C-(2-hydroxyethyl)-3',5'-O-(1,1,3,3-tetraisopropylsiloxan-1,3-diyl)uridine；1-[(6aR,8R,9R,9aS)-9-(2-hydroxyethyl)-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: 171503-88-1
• 化学式: C₂₃H₄₂N₂O₇Si₂
• 分子量: 514.767
• InChiKey: UMQOGORMXGMIJS-KRXUUXHPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  107
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  2'-deoxy-2'-α-C-(2-hydroxyethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine 在 吡啶 作用下， 以 二甲基亚砜 为溶剂， 生成 2'-deoxy-2'-α-C-(2-cyanoethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine
  参考文献：
  名称：

  2'-C-修饰的核苷酸的合成和研究。

  摘要：

  描述了含有2'-脱氧-2'-C-甲基氰基或乙基氰基的尿苷单体的合成。这些单体旨在掺入寡核苷酸中，以研究拟议的由2'链状酰胺基发挥的双链稳定作用。

  DOI：

  10.1081/ncn-100002550
• 作为产物：
  描述：

  1-[(2R,3R,3aS,9aR)-3-(2,3-Dihydroxy-propyl)-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl]-4-hydroxy-1H-pyrimidin-2-one 在 sodium tetrahydroborate 、 sodium periodate 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 1.34h， 生成 2'-deoxy-2'-α-C-(2-hydroxyethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine
  参考文献：
  名称：

  通过具有额外核碱基的寡核苷酸稳定核酸二级结构；2'-脱氧-2'-C-（2-（胸腺嘧啶-1-基）乙基）尿苷的合成和掺入。

  摘要：

  将具有两个核碱基的核苷掺入寡核苷酸中。合成的结构单元2'-脱氧-2'-C-（2-（胸腺嘧啶-1-基）乙基）尿苷2是通过5'，3'-TIPDS保护的2'-脱氧-尿苷由尿苷制备的通过烯丙基的氧化裂解，引入胸腺嘧啶的Mitsunobu反应和适当的脱保护反应来形成2'-C-烯丙啶。将该化合物转化成DMT保护的亚磷酰胺，并一次掺入13-mer寡脱氧核苷酸序列中，一次掺入等位LNA修饰的寡脱氧核苷酸中，并掺入12-mer寡脱氧核苷酸中间四次。这些序列与不同的互补DNA和RNA序列混合，以研究其他核苷酸碱基在双链体，凸起双链体和三向接头中的作用。发现第一个额外的胸腺嘧啶在DNA-RNA双链体中被很好地容纳，而DNA-DNA双链体则稍微不稳定。发现在分支点与附加的胸腺嘧啶的三向连接在DNA-DNA和DNA-RNA环境中均稳定，但在使用修饰的LNA序列时不稳定。然而，在含Mg2 +的缓冲液中，发现三向连接的

  DOI：

  10.1039/b510167k

文献信息

• Synthesis of Nucleosides with Additional Nucleobases
  作者：Charlotte Andersen、S⊘ren L. Pedersen、Poul Nielsen

  DOI：10.1080/15257770701542199

  日期：2007.11.26

  The syntheses of two nucleosides with additional nucleobases in the 2'-position are presented. The nucleosides have two- and one-carbon linkers to the additional nucleobase, respectively. The two nucleosides are synthesized from different strategies. The nucleoside with two carbons in the linker has been incorporated into oligonucleotides and showed stabilization of a tree-way junction.

  提出了两个在2'位置具有附加核苷碱基的核苷的合成。核苷分别具有至另一个核苷碱基的二碳和一碳接头。这两种核苷是从不同的策略合成的。连接子中具有两个碳原子的核苷已被整合到寡核苷酸中，并显示出树状连接的稳定性。
• Synthesis and transcription studies on 5′-triphosphates derived from 2′-C-branched-uridines: 2′-homouridine-5′-triphosphate is a substrate for T7 RNA polymerase
  作者：John B. J. Pavey、Anthony J. Lawrence、Ian A. O'Neil、Stefan Vortler、Richard Cosstick

  DOI：10.1039/b314348a

  日期：——

  The 5'-triphosphates of 2'-hydroxymethyluridine (2'-homouridine) and 2'-hydroxyethyluridine were prepared from the corresponding acetyl-protected nucleosides by initial phosphitylation with 2-chloro-5,6-benzo-1,2,3-dioxaphosphorin-4-one. 2'-Acetamidouridine 5'-triphosphate was prepared in an analogous fashion from uridine 2'-C-, 3'-O-gamma-butyrolactone, in which the 3'-hydroxyl group is internally

  2'-羟基甲基尿苷（2'-高尿嘧啶）和2'-羟基乙基尿苷的5'-三磷酸酯是由相应的乙酰基保护的核苷通过用2-氯-5,6-苯并-1,2,3-进行的磷酸化作用而制备的。二氧磷磷-4-一。由尿苷2′-C-，3′-O-γ-丁内酯以类似的方式制备2′-乙酰胺基尿苷5′-三磷酸酯，其中3′-羟基在内部被保护为内酯。随后用氨处理得到所需的三磷酸乙酰氨基酯。研究了所有三种三磷酸酯作为T7 RNA聚合酶的底物和该酶的Y639F突变体。2' 发现在甲基锰的存在下，三磷酸合尿苷是野生型酶的底物，并且被特异地掺入到短RNA转录物中（长度为20和21个核苷酸）。通过其对碱水解的抗性证实了转录物中存在类似物。凝胶电泳分析还表明，可以将2'-同型尿苷与长度为75个核苷酸的转录物多重结合。这是2'-脱氧2'-α-C分支的5'-三磷酸核苷充当T7 RNA聚合酶底物的首次报道。2'-羟乙基-和2'-乙酰氨基-尿苷三磷酸不是酶
• Sunthesis of functionalised 2′-C-branched nucleosides via their γ-butyrolactones
  作者：Anthony J. Lawrence、John B.J. Pavey、Ian A. O'Neil、Richard Cosstick

  DOI：10.1016/0040-4039(95)01226-8

  日期：1995.8

  Functionalised 2′-C-branched nucleosides that contain either a carboxylic acid (2), a primary amide (3) or a primary hydroxyl (4) group have been prepared and their protection for oligonucleotide synthesis investigated. The 2′-C-3′-O-γ-butyrolactone (5) was also shown to be a useful intermediate for the preparation of these analogues.

  已经制备了包含羧酸（2），伯酰胺（3）或伯羟基（4）的官能化的2'- C-支链核苷，并研究了它们对寡核苷酸合成的保护。还显示了2'- C- 3'- O - γ-丁内酯（5）是制备这些类似物的有用中间体。
• Syntheses of 2′-C-amidoalkyl and 2′-C-cyanoalkyl containing oligodeoxyribonucleotides and assessment of their hybridisation affinity for complementary DNA and RNA
  作者：Lavinia Brennan、Richard Cosstick、Ian A. O'Neil、Arthur Van Aerschot

  DOI：10.1016/j.tet.2006.11.024

  日期：2007.1

  Oligodeoxynucleotides containing 2′-C-branched nucleosides with an amide or nitrile appended to either a one or two carbon alkyl chain have been synthesised. The phosphoramidites of the 2′-C-modified nucleosides were prepared and incorporated into the oligonucleotides using automated DNA synthesis. The duplex stability with complementary RNA and DNA was measured by UV melting experiments, in order

  合成了含有2'- C-支链核苷且酰胺或腈附接到一个或两个碳烷基链上的寡脱氧核苷酸。制备2'- C-修饰的核苷的亚磷酰胺，并使用自动DNA合成将其掺入寡核苷酸中。通过紫外熔解实验测量了具有互补RNA和DNA的双链体稳定性，以评估酰胺/腈功能是否可以在不存在2'-氧的情况下诱导任何双链体稳定性。在没有2'-氧的情况下，含有2'- C-修饰的寡核苷酸的双链体稳定性降低。
• Synthesis and Properties of 2‘-Deoxy-2‘-α-<i>C</i>-branched Nucleosides and Nucleotides
  作者：Anthony J. Lawrence、John B. J. Pavey、Richard Cosstick、Ian A. O'Neil

  DOI：10.1021/jo9614607

  日期：1996.1.1

  Four functionalized 2'-deoxy-2'-alpha-C-branched nucleosides, namely, 2'-deoxy-2'-alpha-C-(carboxymethyl)-uridine, 2'-deoxy-2'-alpha-acetamidouridine, 2'-deoxy-2'-alpha-C-(hydroxyethyl)uridine, and 2'-deoxy-2'-alpha-C-(2,3-dihydroxypropyl)uridine, have been prepared. Conversion of these nucleosides to their appropriately protected phosphoramidites, followed by tetrazole-induced reaction with 2',3'-di-O-acetyluridine, oxidation, and subsequent deprotection furnished the corresponding dinucleoside monophosphates. During the oxidation of the amide-derived phosphite, partial dehydration occurred to give a mixture of the amide- and nitrile-containing dimers. Interestingly, the ratio of amide to nitrile could be largely controlled by choice of oxidant. The hydroxyethyl- and dihydroxypropyl-modified dimers were particularly resistant to snake venom phosphodiesterase-catalyzed hydrolysis (relative half-lives of 129 and 120, respectively, in comparison to UpU). It is anticipated that these nucleoside analogues will ultimately be used in the construction of ribozymes containing enhanced functionality and nuclease resistance.