ethyl 1-phenylcarbonyl-2-[(E)-iodomethylene]cyclopentanecarboxylate | 1092716-91-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 1-phenylcarbonyl-2-[(E)-iodomethylene]cyclopentanecarboxylate
• 英文别名: ethyl (2E)-1-benzoyl-2-(iodomethylidene)cyclopentane-1-carboxylate
• CAS: 1092716-91-0
• 化学式: C₁₆H₁₇IO₃
• 分子量: 384.214
• InChiKey: ZPGKGOQDNSLIOB-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  ethyl 2-phenylcarbonyl-7-iodo-6-heptynoate 在 indium(III) tris[bis(trifluoromethanesulfonyl)amide] 作用下， 以 甲苯 为溶剂， 反应 16.0h， 以91%的产率得到ethyl 1-phenylcarbonyl-2-[(E)-iodomethylene]cyclopentanecarboxylate
  参考文献：
  名称：

  Efficient Formation of Ring Structures Utilizing Multisite Activation by Indium Catalysis

  摘要：

  Lewis acidic indium(III) salts, in particular In(NTf2)(3), effect the conversion of alpha-(omega'-alkynyl)-beta-ketoesters; and omega-alkynyl-beta-ketoesters to the corresponding cyclic products in a manner known as the Coniaene reaction. This reaction can lead to the creation of five- to fifteen-membered-ring carbocycles and heterocycles in good to excellent yields. The synthetic features of the reaction are a relatively low catalyst loading, as low as 0.01 mol % in the best case, as well as no requirement of solvent for five-membered-ring formation and the requirement of only moderately dilute reaction conditions for medium-sized-ring formation. The high reactivity of indium salts is due to the double activation of the beta-ketoester substrate containing an acetylene function. The indium metal activates the beta-ketoester moiety by the formation of an indium enolate, and this indium metal electrophilically activates the alkyne moiety. Such a strong push-pull activation of the substrate by a single metal circumvents the disadvantage of entropic and enthalpic factors generally associated with the formation of medium- and large-sized rings. The reaction allows the ready formation of a fifteen-membered-ring carbocycle, from which di-muscone has been synthesized.

  DOI：

  10.1021/ja805657h