(Z)-2,6-Dimethyl-1,4-dioxabicyclo<11.2.1>tetradeca-2,4,6-trien-12-yne | 154874-05-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (Z)-2,6-Dimethyl-1,4-dioxabicyclo<11.2.1>tetradeca-2,4,6-trien-12-yne
• 英文别名: (2Z)-3,14-dimethyl-5,16-dioxabicyclo[11.2.1]hexadeca-1(15),2,13-trien-7-yne
• CAS: 154874-05-2
• 化学式: C₁₆H₂₀O₂
• 分子量: 244.334
• InChiKey: NYSLODYBOVNPGK-RAXLEYEMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  18
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  22.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-2,6-Dimethyl-1,4-dioxabicyclo<11.2.1>tetradeca-2,4,6-trien-12-yne 在 2,2,6,6-四甲基哌啶 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 、 正戊烷 为溶剂， 反应 0.5h， 以73%的产率得到rel-(2R,3S)-2-(2-Propenyl)-11-methyl-10-oxabicyclo<8.2.1>deca-10,12-dien-4-yn-3-ol
  参考文献：
  名称：

  Synthesis of the pseudopterane 2,5-furanocyclic ring system by [2,3] Wittig ring contraction of bridged furan and dihydrofuran propargylic ethers

  摘要：

  Two routes to the 2,5-furanocyclic ring system of the pseudopterane family of natural products are described. Both employ [2,3] Wittig ring contraction of a 15-membered allylic propargylic ether as the key step. The first route utilizes the bridged 2,5-dihydro furanocyclic ether 24 as the immediate precursor. Treatment with BuLi in THF-pentanes at -78 degrees C affords a 70:30 mixture of trans,anti and trans,syn diastereomers 29 and 31 in 68% yield. The acetate derivatives 30 and 32 are dehydrogenated to furan 33 by MnO2 in ether. In the second route, the furano bridged (Z)-allylic propargylic ether 40Z rearranges to furanocycle 41 in 73% yield upon treatment with LiTMP in; THF-pentane at -78 degrees C.

  DOI：

  10.1021/jo00081a009
• 作为产物：
  描述：

  3-Methyl-2-(4-hydroxy-1-butenyl)furan 在 palladium on activated charcoal 吡啶 、 2,6-二甲基吡啶 、 N,N-二甲基丙烯基脲 、 正丁基锂 、 18-冠醚-6 、 氢气 、 叔丁基锂 、 4-甲基苯磺酸吡啶 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 二异丁基氢化铝 、 甲基磺酰氯 、 lithium chloride 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 甲苯 、 正戊烷 为溶剂， 反应 57.5h， 生成 (Z)-2,6-Dimethyl-1,4-dioxabicyclo<11.2.1>tetradeca-2,4,6-trien-12-yne
  参考文献：
  名称：

  Synthesis of the pseudopterane 2,5-furanocyclic ring system by [2,3] Wittig ring contraction of bridged furan and dihydrofuran propargylic ethers

  摘要：

  Two routes to the 2,5-furanocyclic ring system of the pseudopterane family of natural products are described. Both employ [2,3] Wittig ring contraction of a 15-membered allylic propargylic ether as the key step. The first route utilizes the bridged 2,5-dihydro furanocyclic ether 24 as the immediate precursor. Treatment with BuLi in THF-pentanes at -78 degrees C affords a 70:30 mixture of trans,anti and trans,syn diastereomers 29 and 31 in 68% yield. The acetate derivatives 30 and 32 are dehydrogenated to furan 33 by MnO2 in ether. In the second route, the furano bridged (Z)-allylic propargylic ether 40Z rearranges to furanocycle 41 in 73% yield upon treatment with LiTMP in; THF-pentane at -78 degrees C.

  DOI：

  10.1021/jo00081a009

文献信息

• Synthesis of the pseudopterane 2,5-furanocyclic ring system by [2,3] Wittig ring contraction of bridged furan and dihydrofuran propargylic ethers
  作者：James A. Marshall、Byung-chan Yu

  DOI：10.1021/jo00081a009

  日期：1994.1

  Two routes to the 2,5-furanocyclic ring system of the pseudopterane family of natural products are described. Both employ [2,3] Wittig ring contraction of a 15-membered allylic propargylic ether as the key step. The first route utilizes the bridged 2,5-dihydro furanocyclic ether 24 as the immediate precursor. Treatment with BuLi in THF-pentanes at -78 degrees C affords a 70:30 mixture of trans,anti and trans,syn diastereomers 29 and 31 in 68% yield. The acetate derivatives 30 and 32 are dehydrogenated to furan 33 by MnO2 in ether. In the second route, the furano bridged (Z)-allylic propargylic ether 40Z rearranges to furanocycle 41 in 73% yield upon treatment with LiTMP in; THF-pentane at -78 degrees C.