(-)-(1S,2aS,8bR)-8b-{2-[benzyl(tert-butoxycarbonyl)amino]ethyl}-1-[spiro-(4-γ-butyro-lactonyl)]-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline | 906664-50-4

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (-)-(1S,2aS,8bR)-8b-{2-[benzyl(tert-butoxycarbonyl)amino]ethyl}-1-[spiro-(4-γ-butyro-lactonyl)]-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline
• 英文别名: tert-butyl N-[2-[(1R,2aS,8bR)-2',3-dioxospiro[2a,4-dihydro-2H-cyclobuta[c]quinoline-1,3'-oxolane]-8b-yl]ethyl]-N-benzylcarbamate
• CAS: 906664-50-4
• 化学式: C₂₈H₃₂N₂O₅
• 分子量: 476.572
• InChiKey: SIUJZVAQOJJSAK-FQNJNTOFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  84.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (-)-(1S,2aS,8bR)-8b-{2-[benzyl(tert-butoxycarbonyl)amino]ethyl}-1-[spiro-(4-γ-butyro-lactonyl)]-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 2.33h， 生成 (+)-(1aS,7bS,11aS)-10-benzyl-11a-ethyl-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
• 作为产物：
  描述：

  2-甲烯基丁内酯 、 N-苄基-N-(叔丁氧羰基)-2-(2-氧代-1,2-二氢喹啉-4-基)乙胺 在 chiral complexing agent 作用下， 以 甲苯 为溶剂， 生成 rac-(1S,2aS,8bR)-8b-{2-[benzyl(tert-butoxycarbonyl)amino]ethyl}-1-[spiro-(4-γ-butyro-lactonyl)]-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline 、 (-)-(1S,2aS,8bR)-8b-{2-[benzyl(tert-butoxycarbonyl)amino]ethyl}-1-[spiro-(4-γ-butyro-lactonyl)]-3-oxo-1,2,2a,3,4,8b-hexahydrocyclobuta[c]quinoline
  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