(+/-)-(1α,4α,6α)-1-Butyl-3-methoxy-4-(2-propenyl)bicyclo<4.1.0>hept-2-ene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-(1α,4α,6α)-1-Butyl-3-methoxy-4-(2-propenyl)bicyclo<4.1.0>hept-2-ene
• 英文别名: (1R,4R,6S)-1-butyl-3-methoxy-4-prop-2-enylbicyclo[4.1.0]hept-2-ene
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: VEOHNAYGPBNPAZ-IPYPFGDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (+/-)-(1α,4α,6α)-1-Butyl-3-methoxy-4-(2-propenyl)bicyclo<4.1.0>hept-2-ene 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 0.25h， 以83%的产率得到(+/-)-(1α,4α,6α)-1-Butyl-4-(2-propenyl)bicyclo<4.1.0>heptan-3-one
  参考文献：
  名称：

  Polycyclic Cyclopropanes from Reactions of Alkene-Containing Fischer Carbene Complexes and Alkynes: A Formal Synthesis of (.+-.)-Carabrone

  摘要：

  The polycyclic cyclopropanation reaction of several alkene-containing Fischer carbene complexes with various alkyne partners to provide bicyclo[4.1.0] enol ethers and ketones was examined. A number of features were probed, including the role of carbene donor substituent (amino vs alkoxy), the presence of one vs two pendant alkenes in the carbene complex, the level and sense of diastereoselectivity, and the impact of the substituents present on the alkyne partner. Relative configurations in cyclization products were established by H-1 NMR and difference NOE experiments. Using the above investigations as a guide, the tricyclic sesquiterpene lactone carabrone (5) was formally synthesized. The key cyclization of a symmetrical tetraene-containing carbene complex (8) with propyne provided ketone 42 in good yield as a single diastereomer. Six additional steps gave the tricyclic lactone 6, thus- constituting a formal total synthesis of carabrone (5). Notable features of the synthesis are that (i) the desymmetrizing cyclopropanation reaction between propyne and the symmetrical, tetraene-containing carbene complex is both efficient and highly diastereoselective, (ii) the alkenes remaining after the desymmetrizing cyclopropanation serve very effectively as protected carbonyl groups, and (iii) this work constitutes the first use of a Fischer carbene polycyclic cyclopropanation reaction in natural product synthesis.

  DOI：

  10.1021/jo00118a040
• 作为产物：
  描述：

  1-己炔 、 alkaline earth salt of/the/ methylsulfuric acid 以 苯 为溶剂， 反应 14.0h， 以71%的产率得到(+/-)-(1α,4α,6α)-1-Butyl-3-methoxy-4-(2-propenyl)bicyclo<4.1.0>hept-2-ene
  参考文献：
  名称：

  Polycyclic Cyclopropanes from Reactions of Alkene-Containing Fischer Carbene Complexes and Alkynes: A Formal Synthesis of (.+-.)-Carabrone

  摘要：

  The polycyclic cyclopropanation reaction of several alkene-containing Fischer carbene complexes with various alkyne partners to provide bicyclo[4.1.0] enol ethers and ketones was examined. A number of features were probed, including the role of carbene donor substituent (amino vs alkoxy), the presence of one vs two pendant alkenes in the carbene complex, the level and sense of diastereoselectivity, and the impact of the substituents present on the alkyne partner. Relative configurations in cyclization products were established by H-1 NMR and difference NOE experiments. Using the above investigations as a guide, the tricyclic sesquiterpene lactone carabrone (5) was formally synthesized. The key cyclization of a symmetrical tetraene-containing carbene complex (8) with propyne provided ketone 42 in good yield as a single diastereomer. Six additional steps gave the tricyclic lactone 6, thus- constituting a formal total synthesis of carabrone (5). Notable features of the synthesis are that (i) the desymmetrizing cyclopropanation reaction between propyne and the symmetrical, tetraene-containing carbene complex is both efficient and highly diastereoselective, (ii) the alkenes remaining after the desymmetrizing cyclopropanation serve very effectively as protected carbonyl groups, and (iii) this work constitutes the first use of a Fischer carbene polycyclic cyclopropanation reaction in natural product synthesis.

  DOI：

  10.1021/jo00118a040

文献信息

• Polycyclic Cyclopropanes from Reactions of Alkene-Containing Fischer Carbene Complexes and Alkynes: A Formal Synthesis of (.+-.)-Carabrone
  作者：Thomas R. Hoye、James R. Vyvyan

  DOI：10.1021/jo00118a040

  日期：1995.6

  The polycyclic cyclopropanation reaction of several alkene-containing Fischer carbene complexes with various alkyne partners to provide bicyclo[4.1.0] enol ethers and ketones was examined. A number of features were probed, including the role of carbene donor substituent (amino vs alkoxy), the presence of one vs two pendant alkenes in the carbene complex, the level and sense of diastereoselectivity, and the impact of the substituents present on the alkyne partner. Relative configurations in cyclization products were established by H-1 NMR and difference NOE experiments. Using the above investigations as a guide, the tricyclic sesquiterpene lactone carabrone (5) was formally synthesized. The key cyclization of a symmetrical tetraene-containing carbene complex (8) with propyne provided ketone 42 in good yield as a single diastereomer. Six additional steps gave the tricyclic lactone 6, thus- constituting a formal total synthesis of carabrone (5). Notable features of the synthesis are that (i) the desymmetrizing cyclopropanation reaction between propyne and the symmetrical, tetraene-containing carbene complex is both efficient and highly diastereoselective, (ii) the alkenes remaining after the desymmetrizing cyclopropanation serve very effectively as protected carbonyl groups, and (iii) this work constitutes the first use of a Fischer carbene polycyclic cyclopropanation reaction in natural product synthesis.