ethyl 4-(phenylsulfonyl)-3-butenoate | 134418-79-4

• 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-(phenylsulfonyl)-3-butenoate
• 英文别名: ethyl (E)-4-(benzenesulfonyl)but-3-enoate
• CAS: 134418-79-4
• 化学式: C₁₂H₁₄O₄S
• 分子量: 254.307
• InChiKey: HUKZMANDYPEGAU-UXBLZVDNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 4-(phenylsulfonyl)-3-butenoate 在 rhodium(II) acetate dimer 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 12.17h， 生成 ethyl exo-4-(phenylsulfonyl)bicyclo<3.2.1>octa-2,6-diene-2-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：

  (E)-ethyl 4-(phenylthio)but-2-enoate 在 三乙胺 、 间氯过氧苯甲酸 作用下， 以 氘代苯 为溶剂， 以31%的产率得到ethyl (Z)-4-(benzenesulfonyl)but-3-enoate
  参考文献：
  名称：

  单线态氧在硫化物光氧化过程中引起双键迁移的第一个例子。通过氢过氧sulf叶立德形成砜的实验证据。

  摘要：

  报道了在硫化物的光氧化过程中伴随双键迁移形成砜的第一个例子。提出的证据表明双键迁移不是未重排的砜前体在先的酸催化重排的结果。这种不寻常的观察结果被认为是通过氢过氧sulf内酯中间体的重排形成了砜。

  DOI：

  10.1021/jo016219t

文献信息

• DAVIES, HUW M. L.;CLARK, T. JEFFREY;SMITH, H. DAVID, J. ORG. CHEM., 56,(1991) N2, C. 3817-3824
  作者：DAVIES, HUW M. L.、CLARK, T. JEFFREY、SMITH, H. DAVID

  DOI：——

  日期：——
• 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.
• The First Example of a Singlet Oxygen Induced Double Bond Migration during Sulfide Photooxidation. Experimental Evidence for Sulfone Formation via a Hydroperoxy Sulfonium Ylide
  作者：Edward L. Clennan、David Aebisher

  DOI：10.1021/jo016219t

  日期：2002.2.1

  bond migration during photooxidation of a sulfide is reported. Evidence is presented which demonstrates that the double bond migration is not a result of a prior acid-catalyzed rearrangement of an unrearranged sulfone precursor. This unusual observation is used to argue that the sulfone is formed via rearrangement of a hydroperoxy sulfonium ylide intermediate.

  报道了在硫化物的光氧化过程中伴随双键迁移形成砜的第一个例子。提出的证据表明双键迁移不是未重排的砜前体在先的酸催化重排的结果。这种不寻常的观察结果被认为是通过氢过氧sulf内酯中间体的重排形成了砜。