(1R,4bR,5S,5aR,8aS,9R,9aS,11S)-1,5a,8a,11-tetramethyl-7-methylenedodecahydro-1H,5H-2,4,4b-(epiethane[1,1,2]triyl)-5,9-methanopentaleno[1',6':3,4,1]cyclobuta[1,2-f]indene | 126984-49-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R,4bR,5S,5aR,8aS,9R,9aS,11S)-1,5a,8a,11-tetramethyl-7-methylenedodecahydro-1H,5H-2,4,4b-(epiethane[1,1,2]triyl)-5,9-methanopentaleno[1',6':3,4,1]cyclobuta[1,2-f]indene
• CAS: 126984-49-4
• 化学式: C₁₉H₂₂O₃
• 分子量: 298.382
• InChiKey: VTRXMRRPSKQJNN-DWAGHOTASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.08
• 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：
  0.95
• 拓扑面积：
  57.53
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1R,4bR,5S,5aR,8aS,9R,9aS,11S)-1,5a,8a,11-tetramethyl-7-methylenedodecahydro-1H,5H-2,4,4b-(epiethane[1,1,2]triyl)-5,9-methanopentaleno[1',6':3,4,1]cyclobuta[1,2-f]indene 在 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以74%的产率得到(2R,2aS,2a1S,4R,4aR,4bR,5S,5aS,8aR,9R,9aS,12S)-decahydro-1H,5H-2,4,4b-(epiethane[1,1,2]triyl)-5,9-methanopentaleno[1',6':3,4,1]cyclobuta[1,2-f]indene-1,7,11(8H)-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：

  13,16-exo-anti-3,10-Diacetoxy-15,15-dichlorooctacyclo<10.4.1.1^5,8.0^2,6.0^2,11.0^4,9.0^7,11.0^13,16>octadecan-14-one 在 氢氧化钾 、 氯化铵 、 锌 作用下， 以 甲醇 、 乙醚 为溶剂， 反应 7.25h， 生成 (1R,4bR,5S,5aR,8aS,9R,9aS,11S)-1,5a,8a,11-tetramethyl-7-methylenedodecahydro-1H,5H-2,4,4b-(epiethane[1,1,2]triyl)-5,9-methanopentaleno[1',6':3,4,1]cyclobuta[1,2-f]indene
  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