13,17-exo-syn-Octacyclo<10.5.1.15,8.02,6.02,11.04,9.07,11.013,17>nonadec-15-ene-3,10,14-trione | 136984-00-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 13,17-exo-syn-Octacyclo<10.5.1.15,8.02,6.02,11.04,9.07,11.013,17>nonadec-15-ene-3,10,14-trione
• 英文别名: 13,17-exo-syn-Octacyclo<10.5.1.1^5,8.0^2,6.0^2,11.0^4,9.0^7,11.0^13,17>nonadec-15-ene-3,10,14-trione；13,17-exo-syn-Octacyclo[10.5.1.1^5,8.0^2,6.0^2,11.0^4,9.0^7,11.0^13,17]nonadec-15-ene-3,10,14-trione
• CAS: 136984-00-4
• 化学式: C₁₉H₁₆O₃
• 分子量: 292.334
• InChiKey: UXDFWBMSDWPDOF-YJRBMSHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.27
• 重原子数：
  22.0
• 可旋转键数：
  0.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  51.21
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  13,17-exo-syn-Octacyclo<10.5.1.15,8.02,6.02,11.04,9.07,11.013,17>nonadec-15-ene-3,10,14-trione 650.0 ℃ 、26.66 Pa 条件下， 以36%的产率得到3,7-exo-syn-Hexacyclo<12.2.1.12,8.19,12.03,7.011,15>nonadeca-1(17),5,9(18)-triene-4,10,16-trione
  参考文献：
  名称：

  Roofed polyquinanes: synthesis and electronic structure

  摘要：

  Starting from readily available norbornenobenzoquinone 7 and employing a photothermal metathesis reaction as the main strategy, novel "roofed" polyquinane bisenones 3 and 13 have been synthesized. Among these, the former is potentially serviceable for further elaboration to dodecahedrane 1. Catalytic hydrogenation of 3 provided the dione 12, which fully inscribes the circumference of dodecahedrane sphere. The "roofed" C-16-bisenone 3 has been successfully annulated to C19-bisenone 24 and C19-trisenone 26 by employing the Greene methodology and Pauson-Khand reaction, respectively. The molecular structures of 3 and 13 were computed using molecular mechanics and semiempirical MO methods. The nonbonded distances between the double bonds vary strongly with the method employed. The interactions between the pi-MO's were, therefore, probed by means of photoelectron (PE) spectroscopy. Comparison with the PE spectra of a series of model systems with increasing complexity enabled an unambiguous assignment of the observed peaks. The symmetric and antisymmetric combinations of the pi-MO's of the enone moieties of 3 and 13 show large splittings, characteristic of propano-bridged systems in which through-space and through-bond effects act in concert.

  DOI：

  10.1021/jo00025a019
• 作为产物：
  描述：

  一氧化碳 、 syn-Heptacyclo<10.2.1.1^5,8.0^2,6.0^2,11.0^4,9.0^7,11>hexadec-13-ene-3,10-dione 、 乙炔 在 dicobalt octacarbonyl 作用下， 以 苯 为溶剂， 以64%的产率得到13,17-exo-syn-Octacyclo<10.5.1.15,8.02,6.02,11.04,9.07,11.013,17>nonadec-15-ene-3,10,14-trione
  参考文献：
  名称：

  Roofed polyquinanes: synthesis and electronic structure

  摘要：

  Starting from readily available norbornenobenzoquinone 7 and employing a photothermal metathesis reaction as the main strategy, novel "roofed" polyquinane bisenones 3 and 13 have been synthesized. Among these, the former is potentially serviceable for further elaboration to dodecahedrane 1. Catalytic hydrogenation of 3 provided the dione 12, which fully inscribes the circumference of dodecahedrane sphere. The "roofed" C-16-bisenone 3 has been successfully annulated to C19-bisenone 24 and C19-trisenone 26 by employing the Greene methodology and Pauson-Khand reaction, respectively. The molecular structures of 3 and 13 were computed using molecular mechanics and semiempirical MO methods. The nonbonded distances between the double bonds vary strongly with the method employed. The interactions between the pi-MO's were, therefore, probed by means of photoelectron (PE) spectroscopy. Comparison with the PE spectra of a series of model systems with increasing complexity enabled an unambiguous assignment of the observed peaks. The symmetric and antisymmetric combinations of the pi-MO's of the enone moieties of 3 and 13 show large splittings, characteristic of propano-bridged systems in which through-space and through-bond effects act in concert.

  DOI：

  10.1021/jo00025a019