[(2R,3R,3aS,9aR)-2-(4-Hydroxy-2-oxo-2H-pyrimidin-1-yl)-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-3-yl]-acetaldehyde | 152868-53-6

• 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: [(2R,3R,3aS,9aR)-2-(4-Hydroxy-2-oxo-2H-pyrimidin-1-yl)-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-3-yl]-acetaldehyde
• CAS: 152868-53-6
• 化学式: C₂₃H₄₀N₂O₇Si₂
• 分子量: 512.751
• InChiKey: YJOUABWVNYXYCQ-KRXUUXHPSA-N

物化性质

• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  34.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  108.85
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  [(2R,3R,3aS,9aR)-2-(4-Hydroxy-2-oxo-2H-pyrimidin-1-yl)-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-3-yl]-acetaldehyde 在 sodium chlorite 、 potassium dihydrogenphosphate 、 2-甲基-2-丁烯 作用下， 以 水 、 丙酮 、 叔丁醇 为溶剂， 反应 5.0h， 生成 benzhydryl 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]acetate
  参考文献：
  名称：

  Synthesis and Properties of 2‘-Deoxy-2‘-α-C-branched Nucleosides and Nucleotides

  摘要：

  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.

  DOI：

  10.1021/jo9614607
• 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 periodate 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 0.17h， 生成 [(2R,3R,3aS,9aR)-2-(4-Hydroxy-2-oxo-2H-pyrimidin-1-yl)-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-3-yl]-acetaldehyde
  参考文献：
  名称：

  Synthesis and Properties of 2‘-Deoxy-2‘-α-C-branched Nucleosides and Nucleotides

  摘要：

  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.

  DOI：

  10.1021/jo9614607

文献信息

• Stabilisation of nucleic acid secondary structures by oligonucleotides with an additional nucleobase; synthesis and incorporation of 2′-deoxy-2′-C-(2-(thymine-1-yl)ethyl)uridine
  作者：Søren Ljungberg Pedersen、Poul Nielsen

  DOI：10.1039/b510167k

  日期：——

  A nucleoside with two nucleobases is incorporated into oligonucleotides. The synthetic building block, 2'-deoxy-2'-C-(2-(thymine-1-yl)ethyl)uridine, 2, is prepared from uridine via 5',3'-TIPDS-protected 2'-deoxy-2'-C-allyluridine by an oxidative cleavage of the allyl group, a Mitsunobu reaction for the introduction of thymine and appropriate deprotection reactions. This compound is converted into a

  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
• 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。
• THE SYNTHESIS OF, AND STUDIES ON, 2′-<i>C</i>-MODIFIED NUCLEOTIDES
  作者：Lavinia Brennan、Kevin J. Fettes、Ian A. O'Neil、Richard Cosstick

  DOI：10.1081/ncn-100002550

  日期：2001.3.31

  The synthesis of uridine monomers containing either a 2'-deoxy-2'-C-methylcyano or ethylcyano group is described. These monomers are intended for incorporation into oligonucleotides to investigate a proposed duplex-stabilising effect exerted by 2'-tethered amide groups.

  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。
• 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：——