2'-deoxy-2'-α-C-carboxymethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine | 171503-85-8

• 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-carboxymethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
• 英文别名: 2'-deoxy-2'-α-C-(carboxymethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine；2'-Deoxy-2'-α-C-carboxymethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridene；2-[(6aR,8R,9R,9aS)-8-(2,4-dioxopyrimidin-1-yl)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-9-yl]acetic acid
• CAS: 171503-85-8
• 化学式: C₂₃H₄₀N₂O₈Si₂
• 分子量: 528.75
• InChiKey: FNHHPZFMORXBMR-RPHTVSPISA-N

物化性质

• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  124
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  2'-deoxy-2'-α-C-carboxymethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine 在 ammonium sulfate 、 三甲基氯硅烷 、 三氟甲磺酸三甲基硅酯 、 六甲基二硅氮烷 作用下， 以 乙腈 为溶剂， 反应 22.0h， 生成 5-bromo-2'-deoxy-2'-α-C-carboxymethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
  参考文献：
  名称：

  Studies on 2′-α-C-carboxyalkyl nucleosides and their application to a stereocontrolled nucleobase exchange process

  摘要：

  对2′-α-C-羧基烷基核苷在异常的两步立体控制核苷碱基交换过程中的能力进行了研究。在硅化后，保护的2′-脱氧-2′-α-C-(羧甲基)尿苷衍生物可以通过2′-羧酸基团进行尿嘧啶基团的分子内置换，形成五碳呋喃糖γ-内酯。在相同条件下，同 homologous 2′-脱氧-2′-α-C-(羧乙基)尿苷衍生物并未产生相应的δ-内酯，而是通过尿嘧啶的消除生成相应的糖醇。五碳呋喃糖γ-内酯是通过Vorbrüggen方法进行核苷合成的良好底物，并且与任何嘧啶或嘌呤硅化核苷碱基进行完全选择性的开环反应，从而中等至高产量地生成新型的2′-C-羧甲基β-核苷。

  DOI：

  10.1039/b208786n
• 作为产物：
  描述：

  2'-deoxy-2'-α-C-(2-oxoethyl)-3',5'-O-(1,1,3,3-tetraisopropyldisiloxy)uridine 在 sodium chlorite 、 potassium dihydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 水 、 叔丁醇 为溶剂， 生成 2'-deoxy-2'-α-C-carboxymethyl-3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)uridine
  参考文献：
  名称：

  功能化的2'- C-支链核苷通过其γ-丁内酯的日光浴

  摘要：

  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。

  DOI：

  10.1016/0040-4039(95)01226-8

文献信息

• A novel stereo-controlled nucleobase exchange process for the synthesis of 2′-C-branched nucleosides
  作者：Volker Fehring、Mai Yee Chan、Ian A. O’Neil、Richard Cosstick

  DOI：10.1039/b007099h

  日期：——

  A novel stereo-controlled process is described which enables the uracil base on a 2′-deoxy-2′-α-C-carboxymethyluridine nucleoside to be exchanged for either a purine or another pyrimidine base, via the intermediacy of an isolable pentofuranosyl butyrolactone.

  描述了一种新颖的立体控制过程，使得2′-脱氧-2′-α-C-羧甲基尿苷核苷上的尿嘧啶碱基可以通过可分离的戊糖基丁内酯中间体被替换为嘌呤或另一种嘧啶碱基。
• 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。
• Lawrence, Anthony J.; Pavey, John B. J.; Chan, Mai-Yee, Journal of the Chemical Society. Perkin transactions I, 1997, # 18, p. 2761 - 2767
  作者：Lawrence, Anthony J.、Pavey, John B. J.、Chan, Mai-Yee、Fairhurst, Robin A.、Collingwood, Stephen P.、Fisher, Julie、Cosstick, Richard、O'Neil, Ian A.

  DOI：——

  日期：——
• The Synthesis of 2′-C-Functionalised Nucleosides for Incorporation into Catalytic RNA
  作者：Anthony J. Lawrence、John B. J. Pavey、Ian A. O'Neil、Richard Cosstick

  DOI：10.1080/07328319708006215

  日期：1997.7

  Five 2'-C-functionalized nucleosides (1-5) have been prepared and incorporated into dinucleoside monophosphates. The effect of the functionality on the stability of the adjacent phosphodiester bond toward hydrolysis by nuclease enzymes and extremes of pH has been assessed.
• 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.