(15R,19S)-17,17-dimethyl-16,18-dioxapentacyclo[6.6.5.02,7.09,14.015,19]nonadeca-2,4,6,9,11,13-hexaene

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: (15R,19S)-17,17-dimethyl-16,18-dioxapentacyclo[6.6.5.02,7.09,14.015,19]nonadeca-2,4,6,9,11,13-hexaene
• 化学式: C₁₉H₁₈O₂
• 分子量: 278.351
• InChiKey: OGYWZLRKXZWQGH-OWCVQMPJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  9,10-二氢-9,10-乙烯桥蒽 在 四氧化锇 、 对甲苯磺酸 作用下， 以 吡啶 、 苯 为溶剂， 反应 6.0h， 生成 (15R,19S)-17,17-dimethyl-16,18-dioxapentacyclo[6.6.5.02,7.09,14.015,19]nonadeca-2,4,6,9,11,13-hexaene
  参考文献：
  名称：

  Distortion of Olefin and Carbonyl .pi.-Orbitals in Dibenzobicyclo[2.2.2]octatrienes and Dibenzobicyclo[2.2.2]octadienones. Unsymmetrization of .pi. Lobes Arising from .pi.-.pi. Orbital Interactions

  摘要：

  We have detected the unsymmetrical pi faces of the olefin group in 2-substituted dibenzobicyclo-[2.2.2]octatrienes (2-substituted 9,10-dihydro-9,10-ethenoanthracenes) and the carbonyl groups of 2-substituted and 3-substituted dibenzobicycla[2.2.2]octadienones (2-substituted and 3-substituted 9,10-dihydro-9,10-(11-ketoethano)anthracenes), wherein alpha-type overlaps of the pi orbitals are involved, in a similar manner to longicyclic conjugation. An intrinsically nonequivalent substituent at distal positions modulates the epoxidation and dihydroxylation of the olefin group and the reduction of the carbonyl group. Both systems exhibit similar substituent effects: an ''electron-withdrawing'' substituent such as a nitro or fluoro group gave a large to moderate bias (preferred syn attack with respect to the substituent) whereas an ''electron-donating'' methoxy substituent exhibited a negligible bias. Herein we interpret these biases or nonbiases in terms of unsymmetrization of pi lobes of the olefin and carbonyl pi orbitals, arising from nonequivalent pi-pi interactions rather than from an electron-donating or -withdrawing effect.

  DOI：

  10.1021/jo00093a032

文献信息

• Distortion of Olefin and Carbonyl .pi.-Orbitals in Dibenzobicyclo[2.2.2]octatrienes and Dibenzobicyclo[2.2.2]octadienones. Unsymmetrization of .pi. Lobes Arising from .pi.-.pi. Orbital Interactions
  作者：Tomohiko Ohwada、Iwao Okamoto、Naoki Haga、Koichi Shudo

  DOI：10.1021/jo00093a032

  日期：1994.7

  We have detected the unsymmetrical pi faces of the olefin group in 2-substituted dibenzobicyclo-[2.2.2]octatrienes (2-substituted 9,10-dihydro-9,10-ethenoanthracenes) and the carbonyl groups of 2-substituted and 3-substituted dibenzobicycla[2.2.2]octadienones (2-substituted and 3-substituted 9,10-dihydro-9,10-(11-ketoethano)anthracenes), wherein alpha-type overlaps of the pi orbitals are involved, in a similar manner to longicyclic conjugation. An intrinsically nonequivalent substituent at distal positions modulates the epoxidation and dihydroxylation of the olefin group and the reduction of the carbonyl group. Both systems exhibit similar substituent effects: an ''electron-withdrawing'' substituent such as a nitro or fluoro group gave a large to moderate bias (preferred syn attack with respect to the substituent) whereas an ''electron-donating'' methoxy substituent exhibited a negligible bias. Herein we interpret these biases or nonbiases in terms of unsymmetrization of pi lobes of the olefin and carbonyl pi orbitals, arising from nonequivalent pi-pi interactions rather than from an electron-donating or -withdrawing effect.