(Z)-N-benzoyl-α-dehydro(9-phenanthryl)alanine N'-methylamide | 1391158-06-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (Z)-N-benzoyl-α-dehydro(9-phenanthryl)alanine N'-methylamide
• 英文别名: N-[(Z)-3-(methylamino)-3-oxo-1-phenanthren-9-ylprop-1-en-2-yl]benzamide
• CAS: 1391158-06-7
• 化学式: C₂₅H₂₀N₂O₂
• 分子量: 380.446
• InChiKey: APVRRRQHAQCGCG-KQWNVCNZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  58.2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-N-benzoyl-α-dehydro(9-phenanthryl)alanine N'-methylamide 在 三乙胺 作用下， 以 乙腈 为溶剂， 反应 0.17h， 生成 N-[(E)-3-(methylamino)-3-oxo-1-phenanthren-9-ylprop-1-en-2-yl]benzamide
  参考文献：
  名称：

  Photoinduced Selective Transformation of N-Acyl-α-dehydro(9-phenanthryl)alaninamides into Their Cyclization Intermediates in a Polar Protic Solvent

  摘要：

  Irradiation of the title compounds [(Z)-1] in methanol afforded trans-3,8a-dihydro-2-dibenzo[f,h]quinolinone derivatives (trans-2) in preference to cis-2, all of which serve as precursors of the corresponding 3,4-dihydrodibenzoquinolinones. An analysis of the substituent and solvent effects on the cyclization occuring from the excited-state (E)-1 showed that the reactivity of this (E)-isomer is greatly influenced by the steric bulk of the alkyl group attached to the N'-amide nitrogen of the starting 1. In addition, this analysis confirmed that the stabilization of the excited-state (E)-1 (having a zwitterionic structure), by hydrogen-bonding and charge-transfer interactions with methanol, is an essential prerequisite for the occurrence of the photocyclization reaction selectively forming trans-2 and cis-2.

  DOI：

  10.3987/com-12-12449
• 作为产物：
  描述：

  9-甲醛菲 在 sodium acetate 、 乙酸酐 作用下， 以 四氢呋喃 为溶剂， 生成 (Z)-N-benzoyl-α-dehydro(9-phenanthryl)alanine N'-methylamide
  参考文献：
  名称：

  Photoinduced Selective Transformation of N-Acyl-α-dehydro(9-phenanthryl)alaninamides into Their Cyclization Intermediates in a Polar Protic Solvent

  摘要：

  Irradiation of the title compounds [(Z)-1] in methanol afforded trans-3,8a-dihydro-2-dibenzo[f,h]quinolinone derivatives (trans-2) in preference to cis-2, all of which serve as precursors of the corresponding 3,4-dihydrodibenzoquinolinones. An analysis of the substituent and solvent effects on the cyclization occuring from the excited-state (E)-1 showed that the reactivity of this (E)-isomer is greatly influenced by the steric bulk of the alkyl group attached to the N'-amide nitrogen of the starting 1. In addition, this analysis confirmed that the stabilization of the excited-state (E)-1 (having a zwitterionic structure), by hydrogen-bonding and charge-transfer interactions with methanol, is an essential prerequisite for the occurrence of the photocyclization reaction selectively forming trans-2 and cis-2.

  DOI：

  10.3987/com-12-12449

文献信息

• Photoinduced Selective Transformation of N-Acyl-α-dehydro(9-phenanthryl)alaninamides into Their Cyclization Intermediates in a Polar Protic Solvent
  作者：Tadamitsu Sakurai、Yuki Kawanishi、Hiroko Yoshiie、Tetsutaro Igarashi

  DOI：10.3987/com-12-12449

  日期：——

  Irradiation of the title compounds [(Z)-1] in methanol afforded trans-3,8a-dihydro-2-dibenzo[f,h]quinolinone derivatives (trans-2) in preference to cis-2, all of which serve as precursors of the corresponding 3,4-dihydrodibenzoquinolinones. An analysis of the substituent and solvent effects on the cyclization occuring from the excited-state (E)-1 showed that the reactivity of this (E)-isomer is greatly influenced by the steric bulk of the alkyl group attached to the N'-amide nitrogen of the starting 1. In addition, this analysis confirmed that the stabilization of the excited-state (E)-1 (having a zwitterionic structure), by hydrogen-bonding and charge-transfer interactions with methanol, is an essential prerequisite for the occurrence of the photocyclization reaction selectively forming trans-2 and cis-2.
• Asymmetric Conversion of (Z)-N-Benzoyl-α-dehydro(9-phenanthryl)alanine N´-Methylamide into Its Cyclization Intermediates via Photoinduced Electron Transfer
  作者：Tadamitsu Sakurai、Shin-ichi Matsuki、Kaoru Kawai、Tetsutaro Igarashi、Takayuki Kimura、Shinsaku Hattori

  DOI：10.3987/com-13-12724

  日期：——

  Irradiation of (Z)-N-benzoyl-alpha-dehydro(9-phenanthryl)alanine N'-methylamide [(Z)-1] in 2-propanol-methanol (4:1 v/v) containing (S)-nicotine afforded the (3S,8aS)-3,8a-dihydrodibenzo[f,h]quinolinone derivative [(3S,8aS)-2] and (3R,8aS)-2 in 20% and 35% enantiomeric excess (ee), respectively. Analysis of the effects of a chiral amine and solvent on the electron transfer-initiated enantioselective photocyclization of (Z)-1 revealed that the magnitude of the ee is predominantly determined by the ability of this amine to form hydrogen bonds at the two sites of the enol intermediate as the precursor of 2.