(+)-(1aS,7bS,11aS)-10-benzyl-11a-methyl-1,9,10,11a-tetrahydro-1aH-pyrido[4',3':2,3']-cyclobuta[1,2-c]quinoline-2,11(3H,8H)-dione

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (+)-(1aS,7bS,11aS)-10-benzyl-11a-methyl-1,9,10,11a-tetrahydro-1aH-pyrido[4',3':2,3']-cyclobuta[1,2-c]quinoline-2,11(3H,8H)-dione
• 英文别名: (1R,10S,12S)-14-benzyl-12-methyl-8,14-diazatetracyclo[8.6.0.01,12.02,7]hexadeca-2,4,6-triene-9,13-dione
• 化学式: C₂₂H₂₂N₂O₂
• 分子量: 346.429
• InChiKey: KHYQSXFMHCGGQN-YHYVQYDKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  49.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 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 、 chiral complexing agent 、 氢溴酸 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 5.0h， 生成 (+)-(1aS,7bS,11aS)-10-benzyl-11a-methyl-1,9,10,11a-tetrahydro-1aH-pyrido[4',3':2,3']-cyclobuta[1,2-c]quinoline-2,11(3H,8H)-dione
  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

文献信息

• Photochemistry of 4-(2‘-Aminoethyl)quinolones:  Enantioselective Synthesis of Tetracyclic Tetrahydro-1a<i>H</i>-pyrido[4‘,3‘:2,3]- cyclobuta[1,2-<i>c</i>] Quinoline-2,11(3<i>H</i>,8<i>H</i>)-diones by Intra- and Intermolecular [2 + 2]-Photocycloaddition Reactions in Solution
  作者：Philipp Selig、Thorsten Bach

  DOI：10.1021/jo0606608

  日期：2006.7.1

  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).