(7R,8S)-7,8-epoxy-9,10-dihydrophenantridin-6(5H)-one | 1391132-67-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: (7R,8S)-7,8-epoxy-9,10-dihydrophenantridin-6(5H)-one
• 英文别名: (1aR,9aS)-3,8,9,9a-tetrahydro-1aH-oxireno[2,3-i]phenanthridin-2-one
• CAS: 1391132-67-4
• 化学式: C₁₃H₁₁NO₂
• 分子量: 213.236
• InChiKey: FNDGMUWMXADHFW-JQWIXIFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  16
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-[2-(3-butenoyl)aminophenyl]-4-penten-1-one 在 Grubbs catalyst first generation 、 2,6-二氯吡啶N-氧化物 、 C₅₇H₄₉N₅O₂Ru 、 potassium hydroxide 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 51.0h， 生成 (7R,8S)-7,8-epoxy-9,10-dihydrophenantridin-6(5H)-one
  参考文献：
  名称：

  Enantio- and Regioselective Epoxidation of Olefinic Double Bonds in Quinolones, Pyridones, and Amides Catalyzed by a Ruthenium Porphyrin Catalyst with a Hydrogen Bonding Site

  摘要：

  An array of differently substituted 3-alkenylquinolones was synthesized, and the enantio- and regioselectivity of their Ru-catalyzed epoxidation were studied. A precursor ruthenium(II) complex with a chiral tricyclic gamma-lactam skeleton (octahydro-1H-4,7-methanoisoindol-1-one) was available by Sonogashira cross-coupling with a monobromo-substituted ruthenium(II) porphyrin. Enantioselective epoxidation reactions (60-83% yield, 85-98% ee) were achieved with this catalyst, and it was shown that the enantioselectivity depends critically on the presence of a two-point hydrogen bond interaction between the gamma-lactam site of the catalyst and the delta-lactam (quinolone) site of the substrate. DFT calculations support the hypothesis that the reaction occurs via a hydrogen-bound transition state, in which the 3-alkenylquinolone adopts an s-trans conformation. The calculations further revealed that this transition state is preferred over a competing s-cis transition state because it exerts less strain in the rigid backbone and because the hydrogen bond interaction is more stable. The catalyst loading required for complete conversion was low (<0.2 mol %), and turnover numbers exceeding 4000 were recorded. It was shown that there is little, if any, inhibition of the catalytic process by other quinolones, which could potentially compete with the binding site. A mechanistic model for the catalytic reaction is presented. In accordance with this model 3-alkenylpyridones reacted with similar enantioselectivities as the respective quinolones. The epoxidation products were unstable, however, and the enantiomeric purity (77-87% ee) of the products could be established only after derivatization. Primary alkenoic acid amides also underwent the epoxidation but gave the respective products in lower enantioselectivities (70% and 45% ee), presumably because the enantioface differentiation is hampered by the increased flexibility of the substrates, which exhibit two or three rotatable single bonds between the binding site and the reactive olefinic double bond.

  DOI：

  10.1021/ja305890c

文献信息

• Enantio- and Regioselective Epoxidation of Olefinic Double Bonds in Quinolones, Pyridones, and Amides Catalyzed by a Ruthenium Porphyrin Catalyst with a Hydrogen Bonding Site
  作者：Philipp Fackler、Stefan M. Huber、Thorsten Bach

  DOI：10.1021/ja305890c

  日期：2012.8.1

  An array of differently substituted 3-alkenylquinolones was synthesized, and the enantio- and regioselectivity of their Ru-catalyzed epoxidation were studied. A precursor ruthenium(II) complex with a chiral tricyclic gamma-lactam skeleton (octahydro-1H-4,7-methanoisoindol-1-one) was available by Sonogashira cross-coupling with a monobromo-substituted ruthenium(II) porphyrin. Enantioselective epoxidation reactions (60-83% yield, 85-98% ee) were achieved with this catalyst, and it was shown that the enantioselectivity depends critically on the presence of a two-point hydrogen bond interaction between the gamma-lactam site of the catalyst and the delta-lactam (quinolone) site of the substrate. DFT calculations support the hypothesis that the reaction occurs via a hydrogen-bound transition state, in which the 3-alkenylquinolone adopts an s-trans conformation. The calculations further revealed that this transition state is preferred over a competing s-cis transition state because it exerts less strain in the rigid backbone and because the hydrogen bond interaction is more stable. The catalyst loading required for complete conversion was low (<0.2 mol %), and turnover numbers exceeding 4000 were recorded. It was shown that there is little, if any, inhibition of the catalytic process by other quinolones, which could potentially compete with the binding site. A mechanistic model for the catalytic reaction is presented. In accordance with this model 3-alkenylpyridones reacted with similar enantioselectivities as the respective quinolones. The epoxidation products were unstable, however, and the enantiomeric purity (77-87% ee) of the products could be established only after derivatization. Primary alkenoic acid amides also underwent the epoxidation but gave the respective products in lower enantioselectivities (70% and 45% ee), presumably because the enantioface differentiation is hampered by the increased flexibility of the substrates, which exhibit two or three rotatable single bonds between the binding site and the reactive olefinic double bond.