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 | 185141-83-7

• 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-(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
• 英文别名: 1-[(6aR,8R,9R,9aS)-9-(2,3-dihydroxypropyl)-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: 185141-83-7
• 化学式: C₂₄H₄₄N₂O₈Si₂
• 分子量: 544.793
• InChiKey: IMSNYAIEXMWQMH-OCQIDRNCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.75
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  127
• 氢给体数：
  3
• 氢受体数：
  8

反应信息

• 作为反应物：
  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 吡啶 、 2,6-二甲基吡啶 、 四氮唑 、 sodium chlorite 、 sodium periodate 、 potassium dihydrogenphosphate 、 2-甲基-2-丁烯 、 二异丙基铵盐四氮唑 、 碘 、 triethylamine tris(hydrogen fluoride) 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 、 丙酮 、 乙腈 、 叔丁醇 为溶剂， 反应 23.0h， 生成 benzhydryl 2-[(2R,3R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[2-cyanoethoxy-[[(2R,3R,4R,5R)-3,4-diacetyloxy-5-(2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methoxy]phosphoryl]oxy-2-(2,4-dioxopyrimidin-1-yl)oxolan-3-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-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 四氧化锇 、 N-甲基吗啉氧化物 作用下， 以 丙酮 、 叔丁醇 为溶剂， 反应 1.5h， 生成 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
  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

• 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.
• 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
• 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.