nonacyclo[15.7.7.12,16.01,17.02,10.04,9.011,16.019,24.025,30]dotriaconta-4,6,8,10,19,21,23,25(30)-octaene-3,18-dione | 138723-05-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: nonacyclo[15.7.7.12,16.01,17.02,10.04,9.011,16.019,24.025,30]dotriaconta-4,6,8,10,19,21,23,25(30)-octaene-3,18-dione
• CAS: 138723-05-4
• 化学式: C₃₂H₂₈O₂
• 分子量: 444.573
• InChiKey: VGIPERRKRAHDAE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.0
• 重原子数：
  34.0
• 可旋转键数：
  0.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  34.14
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  o-(1,7-octadiynyl)-α-diazoacetophenone 在 rhodium(II) octanoate 作用下， 以 正戊烷 为溶剂， 反应 6.0h， 以74%的产率得到nonacyclo[15.7.7.12,16.01,17.02,10.04,9.011,16.019,24.025,30]dotriaconta-4,6,8,10,19,21,23,25(30)-octaene-3,18-dione
  参考文献：
  名称：

  Cyclization Reactions of Rhodium Carbene Complexes. Effect of Composition and Oxidation State of the Metal

  摘要：

  Treatment of o-(1,7-octadiynyl)benzoyldiazoethane with rhodium(II) octanoate in pentane resulted in a double internal/internal alkyne insertion reaction producing a labile bicyclo[4.1.0]hept-1(7)ene derivative which readily undergoes a Diels-Alder reaction with diphenylisobenzofuran. Changing the solvent from pentane to CH2Cl2 afforded a 2:1 mixture of cis- and trans-alkenyl-substituted indenones. Stepwise cyclization involving a set of dipolar intermediates occurs in CH2Cl2 whereas metallocyclobutenes are involved when pentane is used as the solvent. The rhodium(II) carboxylate catalyzed reaction of unsymmetrically substituted cyclopropenes gives substituted furans derived from cleavage of the less substituted beta-bond. Thus, treatment of 3-benzoyl-3-methyl-1-(n-butyl)cyclopropene with Rh2OAc4 afforded a 26:1 mixture of 2-phenyl-3-methyl-4-(n-butyl)- and 2-phenyl-3-methyl-5-(n-butyl)furan. In contrast, the [ClRh(CO)(2)](2)-catalyzed reaction resulted in cleavage of the more substituted sigma-bond producing only 2-phenyl-3-methyl-5-(n-butyl)furan. Both reactions involve electrophilic attack of the rhodium metal on the less substituted carbon atom of the cyclopropene pi-bond to give the most stabilized cyclopropyl carbocation. Ring opening followed by rapid electrocyclization to the furan occurs with the Rh(IH) catalyst. With the Rh(I) catalyst, the ring-opened species preferentially cyclizes to a metallocyclobutene intermediate which then equilibrates with the thermodynamically more stable isomer prior to furan formation. The Rh(I)-catalyzed reaction of 3-benzoyl-1-propylcyclopropene with various terminal alkynes gives 4-alkyl-4-propyl-7-phenyloxepins in good yield. These reactions involve electrophilic attack of the rhodium metal on the more substituted carbon of the cyclopropene; pi-bond to give a rhodium carbene complex, This metallo carbenoid undergoes a subsequent [2 + 2] cycloaddition with terminal acetylenes, The resulting rhodacycle rearranges by a formal 1,5-sigmatropic shift, and this is followed by reductive elimination of rhodium to produce the observed oxepin.

  DOI：

  10.1021/jo962271r

文献信息

• Control of chemoselectivity in the rhodium(II)-catalyzed alkyne insertion reaction of .alpha.-diazo ketones
  作者：Albert Padwa、David J. Austin、Simon L. Xu

  DOI：10.1021/jo00031a007

  日期：1992.2

  Chemoselectivity in the rhodium(II) catalyzed reaction of an acetylenic alpha-diazo ketone was found to be markedly influenced by the solvent used. Cyclopropenyl indenones are formed in pentane whereas alkenyl-substituted indenones are produced when CH2Cl2 is used as the solvent.