cis-1α,2α,4α,6α-3,7-dioxatricyclo<4.1.0.0^2,4>heptane | 16326-26-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧环庚烷
• 英文名称: cis-1α,2α,4α,6α-3,7-dioxatricyclo<4.1.0.0^2,4>heptane
• 英文别名: (1RS,2SR,4SR,6RS)-3,6-dioxatricyclo[4.1.0.0^2,4]heptane；cis-1,2,3,4-diepoxycyclopentane；syn-1,2:3,4-Diepoxycyclopentan；cis-1,2:3,4-Diepoxy-cyclopentan；Diepoxycyclopentane, endo-；(1R,2S,4S,6R)-3,7-dioxatricyclo[4.1.0.02,4]heptane
• CAS: 16326-26-4
• 化学式: C₅H₆O₂
• 分子量: 98.1014
• InChiKey: SIWFRAYSJGYECR-VERZDPOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-1α,2α,4α,6α-3,7-dioxatricyclo<4.1.0.0^2,4>heptane 在 吡啶 、 lithium aluminium tetrahydride 、 sodium azide 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 22.0h， 生成 3,7-dibenzoyl-1α,2α,4α,6α-3,7-diazatricyclo<4.1.0.0^2.4>heptane
  参考文献：
  名称：

  Double inversion of the secondary nitrogens incis-Diaziridinocyclopentane

  摘要：

  Abstract1α,2α,4α,6α,‐3,7‐Diazatricyclo[4.1.0.02,4]heptane (cis‐diaziridinocyclopentane) (1) has been prepared from the analogous cis‐diepoxycyclopentane. Ring opening of the diepoxide with sodium azide produced a pair of regioisomeric azido alcohols. Tosylation and treatment with lithium aluminum hydride produced 1. The dibenzoyl derivative possessed the di‐exo stereochemistry for the tertiary aziridine nitrogens. The 1H spectrum of 1 was temperature dependent. Both the CH and NH resonances underwent decoalescence as the temperature was lowered. Because the rate was independent of concentration, the mechanism is probably inversion of the secondary nitrogen, the first such example to occur by the interchange of two diastereotopic, secondary (NH) amine nitrogens within the same molecule. The free energy of activation at coalescence (0 °C) was measured to be 12.8 kcal mol−1. The unsymmetrical slow exchange of 1 is clearly consistent with the exo,endo stereochemistry for the secondary aziridine nitrogens, possibly stabilized by intramolecular attraction.

  DOI：

  10.1002/omr.1270211114
• 作为产物：
  描述：

  环戊二烯内过氧化物 在 (5,10,15,20-tetramethylporphyrinato)cobalt(II) 作用下， 以 四氢呋喃 为溶剂， 生成 cis-1α,2α,4α,6α-3,7-dioxatricyclo<4.1.0.0^2,4>heptane
  参考文献：
  名称：

  Synthesis of 1,2:3,4-diepoxides by catalyzed rearrangement of 1,4-endoperoxides

  摘要：

  DOI：

  10.1021/ja00530a063

文献信息

• Synthesis of (Polyfluoroalkyl)cyclopentenes as Model Compounds for Fluorophilic Cyclopentadienes
  作者：Jaroslav Kvíčala、Tomáš Bříza、Oldřich Paleta、Jan Čermák

  DOI：10.1135/cccc20021345

  日期：——

  Nucleophilic opening of the epoxide ring in 6-oxabicyclo[3.1.0]hexane (1) with ethenylmagnesium bromide was employed for the preparation of 2-ethenylcyclopentan-1-ol (2). Radical addition of perfluoroalkyl iodides 3 to alcohol 2 afforded (polyfluoroiodoalkyl)cyclopentanols 4, which were deiodinated with tributylstannane to (polyfluoroalkyl)cyclopentanols 5, followed by dehydration with Nafion-H to the target (polyfluoroalkyl)cyclopentenes 6, which are potential intermediates for fluorous chemistry. Attempts to synthesize (polyfluoroalkyl)cyclopentadienes or bis(polyfluoroalkyl)cyclopentadienes failed due to the exclusive formation of unexpected side product, polyfluoroiodoalkanol 7, in the course of radical addition of perfluoroalkyl iodides 3 to ethenylcyclopentenol (8) or diethenylcyclopentanediol (9), respectively.

  在6-氧代双环[3.1.0]己烷（1）中，使用乙烯基溴化镁对环氧环进行亲核开启，制备2-乙烯基环戊烷-1-醇（2）。全氟烷基碘化物（3）与醇（2）进行自由基加成反应，得到（全氟烷基碘代基）环戊烷醇（4），再用三丁基锡烷脱碘化得到（全氟烷基）环戊烷醇（5），随后用Nafion-H脱水制备目标产物（全氟烷基）环戊烯（6），这是潜在的氟化学中间体。尝试合成（全氟烷基）环戊二烯或双（全氟烷基）环戊二烯均失败，因为在全氟烷基碘化物（3）与乙烯基环戊烯醇（8）或双乙烯基环戊二醇（9）进行自由基加成反应时，会出现意外的副产物，即多氟烷基碘代醇（7）。
• Polar alicyclic rings: synthesis and structure of all cis-1,2,3,4-tetrafluorocyclopentane
  作者：Zeguo Fang、Nawaf Al-Maharik、Alexandra M. Z. Slawin、Michael Bühl、David O'Hagan

  DOI：10.1039/c6cc01348a

  日期：——

  The all-cis isomer of 1,2,3,4-tetrafluorocyclopentane is prepared and characterised by NMR and X-ray crystallography and the experimental structure compared with theory. The structure has a similarly high polarity to all-cis...

  制备了1,2,3,4-四氟环戊烷的全顺式异构体，并通过NMR和X射线晶体学表征，并与理论比较了实验结构。该结构具有与全顺式类似的高极性。
• Ruthenium(II)-catalyzed reactions of 1,4-epiperoxides
  作者：Masaaki Suzuki、Hiroaki Ohtake、Yoshimi Kameya、Nobuyuki Hamanaka、Ryoji Noyori

  DOI：10.1021/jo00283a023

  日期：1989.10
• Synthesis of 1,2:3,4-diepoxides by catalyzed rearrangement of 1,4-endoperoxides
  作者：Jack D. Boyd、Christopher S. Foote、David K. Imagawa

  DOI：10.1021/ja00530a063

  日期：1980.5
• Ruthenium(II) catalyzed reaction of 1,4-epiperoxides
  作者：M. Suzuki、R. Noyori、N. Hamanaka

  DOI：10.1021/ja00371a041

  日期：1982.4