1-((2R,3R,3aS,9aR)-3-Allyl-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-4-hydroxy-1H-pyrimidin-2-one

• 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: 1-((2R,3R,3aS,9aR)-3-Allyl-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-4-hydroxy-1H-pyrimidin-2-one
• 英文别名: 1-[(6aR,8R,9R,9aS)-2,2,4,4-tetra(propan-2-yl)-9-prop-2-enyl-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]pyrimidine-2,4-dione
• 化学式: C₂₄H₄₂N₂O₆Si₂
• 分子量: 510.778
• InChiKey: UAUOAZQHRNRMNK-YXPKMTABSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.58
• 重原子数：
  34
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  86.3
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  1-((2R,3R,3aS,9aR)-3-Allyl-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 、 臭氧 、 triethylamine tris(hydrogen fluoride) 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 为溶剂， 反应 16.26h， 生成 2'-deoxy-2'-α-C-(acetoxymethyl)uridine
  参考文献：
  名称：

  The synthesis of 2′-homouridine, its incorporation into a dinucleoside monophosphate and hydrolytic behaviour of the dimer

  摘要：

  An efficient route to 2'-homouridine (1), a new nucleoside analogue, is reported that is based on an ene reaction. This nucleoside has been incorporated into a dinucleoside monophosphate and hydrolytic studies on the dimer show that it does not behave like a ribonucleotide. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)01478-6
• 作为产物：
  描述：

  3',5'-O-(1,1,3,3-四异丙基-1,3-二硅氧烷)尿苷 在 吡啶 、 偶氮二异丁腈 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 1-((2R,3R,3aS,9aR)-3-Allyl-5,5,7,7-tetraisopropyl-tetrahydro-1,4,6,8-tetraoxa-5,7-disila-cyclopentacycloocten-2-yl)-4-hydroxy-1H-pyrimidin-2-one
  参考文献：
  名称：

  使用闭环烯烃和烯炔复分解反应合成构象受限的核酸片段

  摘要：

  为了构建用于识别二级 RNA 结构的构象限制性核酸片段，我们合成了不同的含有额外环的单核苷酸和二核苷酸。这些环是通过从已引入双键或三键的核苷酸底物通过闭环烯烃或烯炔复分解反应制备的。

  DOI：

  10.1081/ncn-200060347

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
• Studies on 2′-α-C-carboxyalkyl nucleosides and their application to a stereocontrolled nucleobase exchange process
  作者：Volker Fehring、Sally Knights、Mai-Yee Chan、Ian A. O'Neil、Richard Cosstick

  DOI：10.1039/b208786n

  日期：——

  The ability of 2′-α-C-carboxyalkyl nucleosides to undergo an unusual two-step stereocontrolled nucleobase exchange process has been investigated. Upon silylation a protected 2′-deoxy-2′-α-C-(carboxymethyl)uridine derivative can undergo intramolecular displacement of the uracil base, by the 2′-carboxylic acid group, to form a pentofuranosyl γ-lactone. Under identical conditions the homologous 2′-deoxy-2′-α-C-(carboxyethyl)uridine derivative does not yield the corresponding δ-lactone, but undergoes elimination of uracil to give the corresponding glycal. The pentofuranosyl γ-lactone is a good substrate for nucleoside synthesis by the Vorbrüggen procedures and undergoes completely stereoselective ring opening with either pyrimidine or purine silylated nucleobases to give novel 2′-C-carboxymethyl β-nucleosides in moderate to high yield.

  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。
• Synthesis of 2‘-<i>C</i>-α-(Hydroxyalkyl) and 2‘-<i>C</i>-α-Alkylcytidine Phosphoramidites:  Analogues for Probing Solvent Interactions with RNA
  作者：Nan-Sheng Li、Joseph A. Piccirilli

  DOI：10.1021/jo062002t

  日期：2007.2.1

  Nucleoside analogues bearing 2'-C-alpha-(hydroxyalkyl) and 2'-C-alpha-alkyl substitutes have numerous applications in RNA chemistry and biology. In particular, they provide a strategy to probe the interaction between the 2'-hydroxyl group of RNA and water. To incorporate these nucleoside analogues into oligonucleotides for studies of the group II intron (Gordon, P. M.; Fong, R.; Deb, S.; Li, N.-S.; Schwans, J. P.; Ye, J.-D.; Piccirilli, J. A. Chem. Biol. 2004, 11, 237), we synthesized six new phosphoramidite derivatives of 2'-deoxy-2'-C-alpha-(hydroxyalkyl)cytidine (36: R = -(CH2)(2)OH; 38: R = -(CH2)(3)OH; 40: R = -(CH2)(4)OH) and 2'-deoxy-2'-C-alpha-alkylcytidine (37: R = -CH2CH3; 39: R = -(CH2)(2)CH3; 41: R = -(CH2)(3)CH3) from cytidine or uridine via 2'-C-alpha-allylation, followed by alkene and alcohol transformations. Phosphoramidites 36 and 37 were prepared from cytidine in overall yields of 14% (10 steps) and 7% (11 steps), respectively. Phosphoramidites 38 and 39 were prepared from uridine in overall yields of 30% (10 steps) and 13% (11 steps), respectively. Phosphoramidites 40 and 41 were synthesized from uridine in overall yields of 21% (13 steps) and 25% (14 steps), respectively.
• Groetli, Morten; Undheim, Kjell, Acta Chemica Scandinavica, 1995, vol. 49, # 3, p. 217 - 224
  作者：Groetli, Morten、Undheim, Kjell

  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.