ethyl 4-diazo-4-(phenylsulfonyl)-3-butenoate | 134418-82-9

• 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 4-diazo-4-(phenylsulfonyl)-3-butenoate
• 英文别名: 4-(benzenesulfonyl)-4-diazonio-1-ethoxybuta-1,3-dien-1-olate
• CAS: 134418-82-9
• 化学式: C₁₂H₁₂N₂O₄S
• 分子量: 280.304
• InChiKey: USPUZDQCONEDBK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.21
• 重原子数：
  19.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  96.84
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-(trimethylsiloxy)-1-methoxy-1,3-butadiene 、 ethyl 4-diazo-4-(phenylsulfonyl)-3-butenoate 在 rhodium(II) pivalate 作用下， 以 正戊烷 为溶剂， 以58%的产率得到ethyl 7-methoxy-3-(phenylsulfonyl)-7-<(trimethylsilyl)oxy>cyclohepta-2,5-diene-1-carboxylate
  参考文献：
  名称：

  Versatile synthesis of tropones by reaction of rhodium(II)-stabilized vinylcarbenoids with 1-methoxy-1-[(trimethylsilyl)oxy]buta-1,3-diene

  摘要：

  Rhodium(II)-catalyzed decomposition of vinyldiazomethanes in the presence of 1-methoxy-1-[(trimethylsilyl)oxy]buta-1,3-diene leads to [3 + 4] annulation products by a tandem cyclopropanation/Cope rearrangement sequence. The resulting cycloheptadienes are readily converted to cycloheptatrienones either by hydrolysis with mild acid followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or by treatment with dichloroethoxyoxovanadium. The efficiency of the general strategy was demonstrated through a short synthesis of nezukone.

  DOI：

  10.1021/jo00022a041
• 作为产物：
  描述：

  ethyl 4-(phenylsulfonyl)-3-butenoate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以1.3%的产率得到ethyl 4-diazo-4-(phenylsulfonyl)-3-butenoate
  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

• Stereoselective synthesis of seven-membered carbocycles by a tandem cyclopropanation/Cope rearrangement between rhodium(II)-stabilized vinylcarbenoids and dienes
  作者：Huw M. L. Davies、T. Jeffrey Clark、H. David Smith

  DOI：10.1021/jo00012a011

  日期：1991.6

  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.
• Versatile synthesis of tropones by reaction of rhodium(II)-stabilized vinylcarbenoids with 1-methoxy-1-[(trimethylsilyl)oxy]buta-1,3-diene
  作者：Huw M. L. Davies、T. Jeffrey Clark、Garland F. Kimmer

  DOI：10.1021/jo00022a041

  日期：1991.10

  Rhodium(II)-catalyzed decomposition of vinyldiazomethanes in the presence of 1-methoxy-1-[(trimethylsilyl)oxy]buta-1,3-diene leads to [3 + 4] annulation products by a tandem cyclopropanation/Cope rearrangement sequence. The resulting cycloheptadienes are readily converted to cycloheptatrienones either by hydrolysis with mild acid followed by oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone or by treatment with dichloroethoxyoxovanadium. The efficiency of the general strategy was demonstrated through a short synthesis of nezukone.