(Z)-7-bromo-4'-(methylsulfonyl)-5-heptenophenone | 217454-47-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-7-bromo-4'-(methylsulfonyl)-5-heptenophenone
• 英文别名: (Z)-7-bromo-1-(4-methylsulfonylphenyl)hept-5-en-1-one
• CAS: 217454-47-2
• 化学式: C₁₄H₁₇BrO₃S
• 分子量: 345.257
• InChiKey: XMRXZQOWGWAYEW-HYXAFXHYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (Z)-7-bromo-4'-(methylsulfonyl)-5-heptenophenone 在 indium 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 9.0h， 以38%的产率得到(1S,2S)-1-(4-Methanesulfonyl-phenyl)-2-vinyl-cyclopentanol
  参考文献：
  名称：

  Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes

  摘要：

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.

  DOI：

  10.1021/jo981683s
• 作为产物：
  描述：

  (4-cyanobutyl)triphenylphosphonium bromide 在 盐酸 、 Oxone 、 potassium dihydrogenphosphate 、 溴 、 双(三甲基硅烷基)氨基钾 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 6.25h， 生成 (Z)-7-bromo-4'-(methylsulfonyl)-5-heptenophenone
  参考文献：
  名称：

  Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes

  摘要：

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.

  DOI：

  10.1021/jo981683s

文献信息

• Intramolecular Cyclization of Tethered Phenyl Ketones. Complementary Stereochemical Results Arising from the Indium-Promoted Ring Closure of Allyl Bromides and the Fluoride Ion-Induced Desilylation of Allylsilanes
  作者：Leo A. Paquette、José L. Mendez-Andino

  DOI：10.1021/jo981683s

  日期：1998.11.1

  dThe intramolecular indium-promoted cyclization of 4'-substituted (Z)- and (E)-7-bromo-5-heptenophenones has been examined in aqueous tetrahydrofuran. In every instance, ring closure occurred to deliver the syn-2-vinylcyclopentanol exclusively. The corresponding allylsilanes have been prepared as well, and the course of their fluoride ion-induced cyclization was also studied. In these systems, a kinetic bias for formation of the anti-2-vinylcyclopentanol is observed, although not with the same exclusivity. Accordingly, complementarity in product diastereoselectivity can be realized in purposeful fashion. The data acquired in this investigation suggest that the indium-catalyzed reactions involve intramolecularly coordinated transition states where development of a cis 5/6-bicyclic framework is most energetically feasible. In contrast, the silanes appear to utilize open-chain antiperiplanar transition states. While the latter are not particularly sensitive to double-bond geometry, they are responsive to steric compression involving the aryl group.