(1R,2S,6S,7S)-4,4-dimethyl-3,5,8-trioxatricyclo<5.2.2.0^2,6>undec-10-en-9-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: (1R,2S,6S,7S)-4,4-dimethyl-3,5,8-trioxatricyclo<5.2.2.0^2,6>undec-10-en-9-one
• 英文别名: (1R,2S,6S,7S)-4,4-dimethyl-3,5,8-trioxatricyclo[5.2.2.02,6]undec-10-en-9-one
• 化学式: C₁₀H₁₂O₄
• 分子量: 196.203
• InChiKey: OYRSIXNMTBQURU-VGRMVHKJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R,2S,6S,7S)-4,4-dimethyl-3,5,8-trioxatricyclo<5.2.2.0^2,6>undec-10-en-9-one 在 对甲苯磺酸 作用下， 以 甲醇 为溶剂， 反应 20.0h， 以91%的产率得到methyl (4SR,5RS,6SR)-4,5,6-trihydroxycyclohex-1-enecarboxylate
  参考文献：
  名称：

  Roberts, Stanley M.; Sutton, Peter W., Journal of the Chemical Society. Perkin transactions I, 1995, # 12, p. 1499 - 1504

  摘要：

  DOI：
• 作为产物：
  描述：

  (3aS,7aS)-4-chloro-2,2-dimethyl-3a,7a-dihydro-1,3-benzodioxole 在 三正丁基氢锡 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 (1R,2S,6S,7S)-4,4-dimethyl-3,5,8-trioxatricyclo<5.2.2.0^2,6>undec-10-en-9-one
  参考文献：
  名称：

  二苯乙烯酮与某些环己-3,5-二烯-1,2-顺式-二醇衍生物的反应：将氯苯转化为光学活性的2-氧杂双环[2.2.2]辛烯-3-酮

  摘要：

  二烯11-15与二苯基乙烯酮反应得到的混合物的相应的[2 + 2] -adducts 16-20和[4 + 2] -adducts 21-25：异构体19/24转化成光学活性内酯26在两步。

  DOI：

  10.1039/c39940000803

文献信息

• Reactions of diphenylketene and methylphenylketene with some cis-cyclohexa-3,5-diene-1,2-diol derivatives
  作者：Stanley M. Roberts、Peter W. Sutton、Lorraine Wright

  DOI：10.1039/p19960001157

  日期：——

  The reaction of the dienes 1–5 with diphenylketene to give the [2 + 2]-adducts 6–10 and the [4 + 2]-adducts 11–15, respectively, has been found to occur by an ionic mechanism involving the zwitterion 16. The reactions of the dienes 2 and 3 with methylphenylketene (and also cyclohexa-1,3-diene with diphenylketene) proceed in a similar fashion. The enol ether 13 was converted into the polyoxygenated cyclohexane derivatives 33, 35 and 38.

  与二苯基酮烯反应的二烯体1-5分别生成[2 + 2]加成物6-10和[4 + 2]加成物11-15，已发现该反应通过一种离子机制进行，涉及双性离子16。二烯体2和3与甲基苯基酮烯（以及环己烯-1,3与二苯基酮烯）的反应以类似方式进行。醇醚13转化为多氧化的环己烷衍生物33、35和38。
• Modified Nucleosides for Rna Interference
  申请人：Herdewijn Piet

  公开号：US20080261905A1

  公开（公告）日：2008-10-23

  The present invention relates to the use of modified nucleotides and single or double stranded oligonucleotides having at least one of said modified nucleotides for performing RNA interference. The modified nucleotides are selected from 6-membered ring containing nucleotides such as hexitol, altritol, O-substituted or O-alkylated altritol, cyclohexenyl, ribo-cyclohexenyl and O-substituted or O-alkylated ribo-cyclohexenyl nucleotides. The present invention also relates to novel modified nucleosides or nucleotides and to the use of the novel modified nucleosides and nucleotides in single or double stranded oligonucleotides for RNA interference, antisense therapy or other applications.

  本发明涉及使用修饰核苷酸和至少含有其中一种修饰核苷酸的单链或双链寡核苷酸来进行RNA干扰。修饰核苷酸从包含六元环的核苷酸中选择，例如己糖醇，阿尔特糖醇，O-取代或O-烷基化的阿尔特糖醇，环己烯基，核糖-环己烯基和O-取代或O-烷基化的核糖-环己烯基核苷酸。本发明还涉及新型修饰核苷或核苷酸以及在单链或双链寡核苷酸中使用新型修饰核苷和核苷酸进行RNA干扰、反义治疗或其他应用。
• Synthesis and Conformational Analysis of a Ribo-Type Cyclohexenyl Nucleoside
  作者：Sara Vijgen、Koen Nauwelaerts、Jing Wang、Arthur Van Aerschot、Irene Lagoja、Piet Herdewijn

  DOI：10.1021/jo048037f

  日期：2005.6.1

  straightforward approach to a novel class of ribo-type cyclohexenyl nucleosides is described. An electron-demand Diels−Alder reaction forms the key-step of the chosen synthetic pathway. Although the difference is small, conformational analysis using NMR shows that this nucleoside analogue adopts preferentially an 2H3 conformation (S-type), while the “deoxy” cyclohexenyl analogue has a preference for a C3‘ endo conformation

  描述了一种新颖的核糖型环己烯基核苷类的直接方法。电子需求的Diels-Alder反应形成了所选合成途径的关键步骤。尽管差异很小，但使用NMR进行的构象分析表明，该核苷类似物优先采用2 H 3构象（S型），而“脱氧”环己烯基类似物优先选择C3'内构象（N型）。构象平衡的分析表明，在给定的实验条件下，腺苷与其环己烯基同源物之间的差异在于它们的不同ΔG价值观 此外，在腺苷中，构象偏好是焓起源的，而在环己烯基同源物中，构象偏好是熵的起源的。
• 3-bromo-2-pyrone: an easily prepared chameleon diene and a synthetic equivalent of 2-pyrone in thermal diels-alder cycloadditions
  作者：Gary H. Posner、Todd D. Nelson、Chris M. Kinter、Kamyar Afarinkia

  DOI：10.1016/s0040-4039(00)92368-2

  日期：1991.9

  3-Bromo-2-pyrone, a stable solid prepared by a new route (eq. 1), has been found to undergo smooth and regiospecific 2+4-cycloadditions between 78-90-degrees-C with both electron-rich and electron-deficient dienophiles; subsequent high-yield reductive debrominations produced halogen-free cycloadducts thus showing 3-bromo-2-pyrone to be a practical and effective synthetic equivalent of 2-pyrone in thermal Diels-Alder cycloadditions.