(Z)-11-Methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene | 141398-24-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: (Z)-11-Methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene
• 英文别名: (5Z)-11-methyl-13-oxabicyclo[8.2.1]trideca-1(12),5,10-triene
• CAS: 141398-24-5
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: ASCODJBJARKJQO-IHWYPQMZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  13.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (Z)-11-Methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene 以 氯仿 为溶剂， 反应 52.0h， 以100%的产率得到
  参考文献：
  名称：

  Synthesis of 2,5-furanocycles through intraannular cyclization of macrocyclic allenones

  摘要：

  A new approach to 2,5-bridged furanocyclic compounds was demonstrated for rings of 12-14 members. Accordingly, allenylstannyl aldehydes 1.16, 2.11, 3.12a, 3.12b, 4.12, 5.15, and 6.12, upon treatment with BF3.OEt2 at -78-degrees-C, smoothly cyclized to the homopropargylic alcohols 1.17, 2.12,3.13a, 3.13b, 4.13,5.16, and 6.13 in 87-94% yield. Oxidation and basic isomerization afforded the allenones 1.19, 2.14, 3.15a, 3.15b, 4.14, 5.18, and 6.15 in high yield. Intraannular cyclization to the furanocycles 1.21, 2.15, 3.16a, 3.16b, 4.16, 5.19, and 6.16 was effected with catalytic AgNO3 and CaCO3 in aqueous acetone. Furanocycles 1.21, 2.15, 3.16a, and 3.16b, with an appropriately disposed transannular (Z)-double bond, underwent facile intramolecular Diels-Alder cyclization in over 90% yield. The 12-membered furanocycles 4.16 and 5.19 with a transannular (E) double bond did not cyclize but instead were oxidized by the AgNO3 catalyst to macrocyclic enediones 4.17 and 5.20. These unusual furan reactions are presumably facilitated by ring strain (furan bending) in accord with molecular mechanics calculations.

  DOI：

  10.1021/jo00038a029
• 作为产物：
  描述：

  (Z)-2-methyl-2,3,8-cyclododecatrienone 在 silver nitrate 、 calcium carbonate 作用下， 以 水 、 丙酮 为溶剂， 反应 3.0h， 以38%的产率得到(Z)-11-Methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene
  参考文献：
  名称：

  Synthesis of 2,5-furanocycles through intraannular cyclization of macrocyclic allenones

  摘要：

  A new approach to 2,5-bridged furanocyclic compounds was demonstrated for rings of 12-14 members. Accordingly, allenylstannyl aldehydes 1.16, 2.11, 3.12a, 3.12b, 4.12, 5.15, and 6.12, upon treatment with BF3.OEt2 at -78-degrees-C, smoothly cyclized to the homopropargylic alcohols 1.17, 2.12,3.13a, 3.13b, 4.13,5.16, and 6.13 in 87-94% yield. Oxidation and basic isomerization afforded the allenones 1.19, 2.14, 3.15a, 3.15b, 4.14, 5.18, and 6.15 in high yield. Intraannular cyclization to the furanocycles 1.21, 2.15, 3.16a, 3.16b, 4.16, 5.19, and 6.16 was effected with catalytic AgNO3 and CaCO3 in aqueous acetone. Furanocycles 1.21, 2.15, 3.16a, and 3.16b, with an appropriately disposed transannular (Z)-double bond, underwent facile intramolecular Diels-Alder cyclization in over 90% yield. The 12-membered furanocycles 4.16 and 5.19 with a transannular (E) double bond did not cyclize but instead were oxidized by the AgNO3 catalyst to macrocyclic enediones 4.17 and 5.20. These unusual furan reactions are presumably facilitated by ring strain (furan bending) in accord with molecular mechanics calculations.

  DOI：

  10.1021/jo00038a029