(Z)-2-methyl-2,3,8-cyclododecatrienone | 141398-23-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-2-methyl-2,3,8-cyclododecatrienone
• CAS: 141398-23-4
• 化学式: C₁₃H₁₈O
• 分子量: 190.285
• InChiKey: SDSDXZJBRRQYNZ-ATPLWMGHSA-N

反应信息

• 作为反应物：
  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
• 作为产物：
  描述：

  (Z)-methyl-8-cyclododecen-3-yn-1-ol 在 戴斯-马丁氧化剂 、 三乙胺 作用下， 生成 (Z)-2-methyl-2,3,8-cyclododecatrienone
  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