ethyl (E)-2-diazo-6-phenyl-1-hexa-3,5-dienoate | 126554-34-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl (E)-2-diazo-6-phenyl-1-hexa-3,5-dienoate
• CAS: 126554-34-5
• 化学式: C₁₄H₁₄N₂O₂
• 分子量: 242.277
• InChiKey: APVYLRRXUCAITH-DPWZYIFFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.49
• 重原子数：
  18.0
• 可旋转键数：
  5.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  62.7
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2,4-二甲基-1,3-戊二烯 、 ethyl (E)-2-diazo-6-phenyl-1-hexa-3,5-dienoate 在 rhodium(II) hexanoate 作用下， 以 二氯甲烷 为溶剂， 以59%的产率得到ethyl 4,4,6-trimethyl-3-((E)-2-phenylethenyl)cyclohepta-1,5-diene-1-carboxylate
  参考文献：
  名称：

  Stereoselective synthesis of seven-membered carbocycles by a tandem cyclopropanation/Cope rearrangement between rhodium(II)-stabilized vinylcarbenoids and dienes

  摘要：

  Rhodium (II)-catalyzed decomposition of vinyldiazomethanes in the presence of dienes generated 1,4-cycloheptadienes by a tandem cyclopropanation/Cope rearrangement. Excellent stereocontrol of up to three stereogenic centers in the cycloheptadienes was achieved. The stereoselectivity of the initial cyclopropanation ranged from 4:1 to > 20:1, favoring cis-divinylcyclopropanes, and good regiocontrol was observed in the cyclopropanation of unsymmetrical dienes. Unless sterically encumbered, the cis-divinylcyclopropanes rearranged cleanly to cycloheptadienes under the reaction conditions. The trans-divinylcyclopropanes, when formed, were sufficiently stable to be observed in the crude reaction mixtures, but most were prone to facile 1,5-homodienyl rearrangements.

  DOI：

  10.1021/jo00012a011
• 作为产物：
  描述：

  3,5-己二烯酸,6-苯基-,乙基酯,(E,E)- 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以56%的产率得到ethyl (E)-2-diazo-6-phenyl-1-hexa-3,5-dienoate
  参考文献：
  名称：

  Stereoselective synthesis of seven-membered carbocycles by a tandem cyclopropanation/Cope rearrangement between rhodium(II)-stabilized vinylcarbenoids and dienes

  摘要：

  Rhodium (II)-catalyzed decomposition of vinyldiazomethanes in the presence of dienes generated 1,4-cycloheptadienes by a tandem cyclopropanation/Cope rearrangement. Excellent stereocontrol of up to three stereogenic centers in the cycloheptadienes was achieved. The stereoselectivity of the initial cyclopropanation ranged from 4:1 to > 20:1, favoring cis-divinylcyclopropanes, and good regiocontrol was observed in the cyclopropanation of unsymmetrical dienes. Unless sterically encumbered, the cis-divinylcyclopropanes rearranged cleanly to cycloheptadienes under the reaction conditions. The trans-divinylcyclopropanes, when formed, were sufficiently stable to be observed in the crude reaction mixtures, but most were prone to facile 1,5-homodienyl rearrangements.

  DOI：

  10.1021/jo00012a011

文献信息

• Novel entry to the tropane system by reaction of rhodium(II) acetate stabilized vinylcarbenoids with pyrroles
  作者：Huw M.L. Davies、Wendy B. Young、H.David Smith

  DOI：10.1016/s0040-4039(01)80766-8

  日期：1989.1

  Rhodium(II) acetate catalyzed decomposition of vinyldiazomethanes in the presence of N-alkoxycarbonylpyrroles provides a direct entry to the skeleton of tropane alkaloids. Similar reactions with N-alkylpyrroles result in the formation of alkylation products.

  在N-烷氧基羰基吡咯的存在下，乙酸铑（II）催化的乙烯基重氮甲烷的分解提供了直接进入托烷生物碱骨架的入口。与N-烷基吡咯的类似反应导致烷基化产物的形成。
• Stereoselective cyclopropanations with vinylcarbenoids
  作者：Huw M.L Davies、T.Jeffrey Clark、Linda A Church

  DOI：10.1016/s0040-4039(01)93446-x

  日期：——

  Rhodium(II) acetate catalyzed decomposition of vinyldiazomethanes in the presence of alkenes results in cyclopropanation with a high degree of stereoselectivity.

  在烯烃存在下乙酸铑（II）催化乙烯基重氮甲烷的分解导致具有高度立体选择性的环丙烷化。