4-[2-(4-methoxybenzylamino)ethyl]-2(1H)-quinolone | 906664-07-1

• 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: 4-[2-(4-methoxybenzylamino)ethyl]-2(1H)-quinolone
• 英文别名: 4-[2-[(4-methoxyphenyl)methylamino]ethyl]-1H-quinolin-2-one
• CAS: 906664-07-1
• 化学式: C₁₉H₂₀N₂O₂
• 分子量: 308.38
• InChiKey: YAEHNWNFKZCMBA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  50.4
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-[2-(4-methoxybenzylamino)ethyl]-2(1H)-quinolone 在 三乙胺 、 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 2.0h， 生成 methyl rac-(1S,2aS,8bR)-8b-{2-[(4-methoxybenzyl)amino]ethyl}-1-methyl-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline-1-carboxylate
  参考文献：
  名称：

  Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1aH-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-c] Quinoline-2,11(3H,8H)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution

  摘要：

  Enantioselective [2 + 2]-photocycloaddition reactions on 4-(2'-aminoethyl) quinolones in solution were studied using the enantiomerically pure complexing agent 1 as source of chirality. The intermolecular reactions of fully N-protected substrates 5a-5c with different 2-alkyl-substituted acrylates 12-15 represent the first systematic study on the diastereoselectivity of their intermolecular [2 + 2]-photocycloadditions to unsymmetrically 1,1-disubstituted olefins (75-91% yield, d.r. = 58/42-95/5). N-Benzylic-protected photoproducts exo-16a/b-19a/b could easily be converted into lactams 20a/b-23a/b by a sequence of Boc deprotection and thermal lactamization (74-98% yield). Identical products 20a-22a were directly accessible by the intramolecular [ 2 + 2]-photocycloaddition of acrylic acid amides 2-4 (41-61% yield). The suitability of both pathways for an enantioselective reaction variant was proven (70-92% ee). Thus, tetracyclic lactams possessing the carbon framework C were obtained with good yields and enantio-selectivities of up to 92% ee in intramolecular reactions. Comparative investigation of both routes showed that quinolone dimerization was the single most decisive factor preventing a complete chirality transfer. Functional group manipulations were successfully conducted with the primary photoproduct exo-17a. Finally, a new and unexpected type of benzylic hydrogen abstraction-radical cyclization reaction was discovered for substrate 5a, which explains the photochemical instability of substrates 2-5 under short wavelength irradiation (lambda = 300 nm).

  DOI：

  10.1021/jo0606608
• 作为产物：
  描述：

  2-羟基-4-甲基喹啉 在 lithium aluminium tetrahydride 、 正丁基锂 、 氯化亚砜 、 氢溴酸 作用下， 反应 0.5h， 生成 4-[2-(4-methoxybenzylamino)ethyl]-2(1H)-quinolone
  参考文献：
  名称：

  Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1aH-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-c] Quinoline-2,11(3H,8H)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution

  摘要：

  Enantioselective [2 + 2]-photocycloaddition reactions on 4-(2'-aminoethyl) quinolones in solution were studied using the enantiomerically pure complexing agent 1 as source of chirality. The intermolecular reactions of fully N-protected substrates 5a-5c with different 2-alkyl-substituted acrylates 12-15 represent the first systematic study on the diastereoselectivity of their intermolecular [2 + 2]-photocycloadditions to unsymmetrically 1,1-disubstituted olefins (75-91% yield, d.r. = 58/42-95/5). N-Benzylic-protected photoproducts exo-16a/b-19a/b could easily be converted into lactams 20a/b-23a/b by a sequence of Boc deprotection and thermal lactamization (74-98% yield). Identical products 20a-22a were directly accessible by the intramolecular [ 2 + 2]-photocycloaddition of acrylic acid amides 2-4 (41-61% yield). The suitability of both pathways for an enantioselective reaction variant was proven (70-92% ee). Thus, tetracyclic lactams possessing the carbon framework C were obtained with good yields and enantio-selectivities of up to 92% ee in intramolecular reactions. Comparative investigation of both routes showed that quinolone dimerization was the single most decisive factor preventing a complete chirality transfer. Functional group manipulations were successfully conducted with the primary photoproduct exo-17a. Finally, a new and unexpected type of benzylic hydrogen abstraction-radical cyclization reaction was discovered for substrate 5a, which explains the photochemical instability of substrates 2-5 under short wavelength irradiation (lambda = 300 nm).

  DOI：

  10.1021/jo0606608