dimethyl (1α,8α,9β,10α,12α,13β)-11,11-dimethoxypentacyclo[6.5.1.0^2,7.0^9,13.0^10,12]tetradeca-2,4,6-triene-10,12-dicarboxylate | 324033-77-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: dimethyl (1α,8α,9β,10α,12α,13β)-11,11-dimethoxypentacyclo[6.5.1.0^2,7.0^9,13.0^10,12]tetradeca-2,4,6-triene-10,12-dicarboxylate
• 英文别名: dimethyl (1S,8R,9S,10S,12R,13R)-11,11-dimethoxypentacyclo[6.5.1.02,7.09,13.010,12]tetradeca-2,4,6-triene-10,12-dicarboxylate
• CAS: 324033-77-4
• 化学式: C₂₀H₂₂O₆
• 分子量: 358.391
• InChiKey: ATGFDFZTJKEIMD-OGBLJDROSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  dimethyl (1α,8α,9β,10α,12α,13β)-11,11-dimethoxypentacyclo[6.5.1.0^2,7.0^9,13.0^10,12]tetradeca-2,4,6-triene-10,12-dicarboxylate 在 三氟乙酸 作用下， 以 氯仿 、 水 为溶剂， 反应 20.0h， 以50%的产率得到trimethyl (1α,8α,9β,11α,12β)-tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6-triene-10,10,11-tricarboxylate
  参考文献：
  名称：

  摘要：

  Dimethoxycarbene, generated from 2,2- dimethoxy- 5,5- dimethyl-Delta (3)-1,3,4-oxadiazoline (8), adds to the electron-deficient double bond of ring-fused cyclobutene diesters (11), (12) and (15) from the face remote from the methano bridge to give the respective bicyclo[2.1.0] pentanone acetals (13), (14) and (16). In two cases, dimethylcyclopropanes (17) and (24) also formed as by-products in these reactions. Mechanisms for the formation of all products and by-products are proposed, especially in regard to an unusual 1,3-dipolar cycloaddition product (23) isolated from the reaction of (8) with (11). Hydrolysis of acetal (13) to the ring-fused cyclopropanone (27) is thwarted by preferential release of ring strain of an external cyclopropyl carbon-carbon bond. In acid media this results in the formation of a benzonorbornane-fused cyclobutane triester (26) with proton capture from the same face, likely from concerted methoxy group-assisted opening of the three-membered ring. Kinetic product (26) is isomerized to the thermodynamic isomer (30) with sodium methoxide. Attempted deacetalization of (13) with iodotrimethylsilane gives (26) when traces of acid are present, but provides the thermodynamic product (30) directly in the presence of pyridine.

  DOI：

  10.1071/ch00077
• 作为产物：
  描述：

  dimethyl 1α,8α,9β,12β-tetracyclo[6.4.1.0^2,7.0^9,12]trideca-2,4,6,10-tetraene-10,11-dicarboxylate 、 2,5-dihydro-2,2-dimethoxy-5,5-dimethyl-1,3,4-oxadiazole 以 甲苯 为溶剂， 反应 25.0h， 以67%的产率得到dimethyl (1α,8α,9β,10α,12α,13β)-11,11-dimethoxypentacyclo[6.5.1.0^2,7.0^9,13.0^10,12]tetradeca-2,4,6-triene-10,12-dicarboxylate
  参考文献：
  名称：

  摘要：

  Dimethoxycarbene, generated from 2,2- dimethoxy- 5,5- dimethyl-Delta (3)-1,3,4-oxadiazoline (8), adds to the electron-deficient double bond of ring-fused cyclobutene diesters (11), (12) and (15) from the face remote from the methano bridge to give the respective bicyclo[2.1.0] pentanone acetals (13), (14) and (16). In two cases, dimethylcyclopropanes (17) and (24) also formed as by-products in these reactions. Mechanisms for the formation of all products and by-products are proposed, especially in regard to an unusual 1,3-dipolar cycloaddition product (23) isolated from the reaction of (8) with (11). Hydrolysis of acetal (13) to the ring-fused cyclopropanone (27) is thwarted by preferential release of ring strain of an external cyclopropyl carbon-carbon bond. In acid media this results in the formation of a benzonorbornane-fused cyclobutane triester (26) with proton capture from the same face, likely from concerted methoxy group-assisted opening of the three-membered ring. Kinetic product (26) is isomerized to the thermodynamic isomer (30) with sodium methoxide. Attempted deacetalization of (13) with iodotrimethylsilane gives (26) when traces of acid are present, but provides the thermodynamic product (30) directly in the presence of pyridine.

  DOI：

  10.1071/ch00077