(E)-4-Methoxymethoxy-12-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene | 136893-78-2

• 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: (E)-4-Methoxymethoxy-12-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene
• 英文别名: (5E)-4-(methoxymethoxy)-12-methyl-13-oxabicyclo[8.2.1]trideca-1(12),5,10-triene
• CAS: 136893-78-2
• 化学式: C₁₅H₂₂O₃
• 分子量: 250.338
• InChiKey: LFFNVBCSKXQBKU-GQCTYLIASA-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：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  31.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-4-Methoxymethoxy-12-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),5,10-triene 在 水 、 silver nitrate 作用下， 以 丙酮 为溶剂， 生成 (2Z,8E)-10-Methoxymethoxy-2-methyl-cyclododeca-2,8-diene-1,4-dione
  参考文献：
  名称：

  Synthesis of macrocyclic homopropargylic alcohols through intramolecular SE' addition of allenylstannanes and their subsequent conversion to 2,5-furanocycles

  摘要：

  The 2,5-furanocyclododecenes 16, 20, and 24 have been prepared by a new route involving intramolecular S(E)' addition of propargylic stannanes 3, 6, and 9 then exposure of the derived allenones 14, 19, and 23 to AgN-O3-CaCO3 in aqueous acetone at room temperature.

  DOI：

  10.1021/jo00022a008
• 作为产物：
  描述：

  (E)-2-methyl-9-(methoxymethoxy)-2,3,8-cyclododecatriene 在 silver nitrate 、 calcium carbonate 作用下， 以 水 、 丙酮 为溶剂， 反应 4.0h， 以91%的产率得到(E)-4-Methoxymethoxy-12-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

文献信息

• Synthesis of macrocyclic homopropargylic alcohols through intramolecular SE' addition of allenylstannanes and their subsequent conversion to 2,5-furanocycles
  作者：James A. Marshall、Xiao Jun Wang

  DOI：10.1021/jo00022a008

  日期：1991.10

  The 2,5-furanocyclododecenes 16, 20, and 24 have been prepared by a new route involving intramolecular S(E)' addition of propargylic stannanes 3, 6, and 9 then exposure of the derived allenones 14, 19, and 23 to AgN-O3-CaCO3 in aqueous acetone at room temperature.
• Synthesis of 2,5-furanocycles through intraannular cyclization of macrocyclic allenones
  作者：James A. Marshall、Xiao Jun Wang

  DOI：10.1021/jo00038a029

  日期：1992.6

  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.