(3aS,3bS,9bS)-1-[N'-(tert-butoxycarbonyl)-N-(3-methylbut-2-enyl)carbamimidoyl]-4-{3-[1,2-di(tert-butoxycarbonyl)-3-(3-methylbut-2-enyl)guanidino]propyl}-2,3,3a,4,5,9b-hexahydro-4-(3-hydroxypropyl)-1H-pyrrolo[3,2-c]quinoline-8-carboxylic acid | 489426-36-0

• 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: (3aS,3bS,9bS)-1-[N'-(tert-butoxycarbonyl)-N-(3-methylbut-2-enyl)carbamimidoyl]-4-{3-[1,2-di(tert-butoxycarbonyl)-3-(3-methylbut-2-enyl)guanidino]propyl}-2,3,3a,4,5,9b-hexahydro-4-(3-hydroxypropyl)-1H-pyrrolo[3,2-c]quinoline-8-carboxylic acid
• 英文别名: (3As,4S,9bS)-1-[N'-(3-methylbut-2-enyl)-N-[(2-methylpropan-2-yl)oxycarbonyl]carbamimidoyl]-4-[3-[[N'-(3-methylbut-2-enyl)-N-[(2-methylpropan-2-yl)oxycarbonyl]carbamimidoyl]amino]propyl]-2,3,3a,4,5,9b-hexahydropyrrolo[3,2-c]quinoline-8-carboxylic acid
• CAS: 489426-36-0
• 化学式: C₃₇H₅₇N₇O₆
• 分子量: 695.903
• InChiKey: XPUWQPOXSLPQKW-DNCXPJJSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  50
• 可旋转键数：
  17
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  166
• 氢给体数：
  5
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (3aS,3bS,9bS)-1-[N'-(tert-butoxycarbonyl)-N-(3-methylbut-2-enyl)carbamimidoyl]-4-{3-[1,2-di(tert-butoxycarbonyl)-3-(3-methylbut-2-enyl)guanidino]propyl}-2,3,3a,4,5,9b-hexahydro-4-(3-hydroxypropyl)-1H-pyrrolo[3,2-c]quinoline-8-carboxylic acid 在 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以27.8 mg的产率得到(-)-martinellic acid
  参考文献：
  名称：

  通过自由基加成-环化-消除反应全合成（-）-马来酸

  摘要：

  描述了天然存在的第一种吡咯并[3,2- c ]喹啉生物碱马汀酸的不对称全合成。我们合成（-）-马来酸的三个关键步骤是肟醚与α，β-不饱和酯的Bu 3 SnH促进的自由基加成-环化-消除（RACE）反应，生成吡咯并[3,2 - c ^ ]喹啉核，化学选择性内酰胺羰基还原，和胍基化Mitsunobu反应条件下进行。还使用SmI 2研究了关键的自由基环化反应。（-）-Martinellic acid由市售的4-溴-3-甲基苯甲酸甲酯以比以前的合成更少的步骤合成，并且总产率得到了提高。

  DOI：

  10.1021/jo800560p
• 作为产物：
  描述：

  methyl (3aS,4S,9bS)-2,3,3a,4,5,9b-hexahydro-5-(3-oxobutanoyl)-1-(phenylmethyl)-1H-pyrrolo-[3,2-c]quinoline-8-carboxylate 在 吡啶 、 盐酸 、 sodium azide 、 水 、 氢气 、 sodium methylate 、 palladium(II) hydroxide 、 silver nitrate 、 三乙胺 、 sodium hydroxide 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 40.0 ℃ 、101.33 kPa 条件下， 反应 102.5h， 生成 (3aS,3bS,9bS)-1-[N'-(tert-butoxycarbonyl)-N-(3-methylbut-2-enyl)carbamimidoyl]-4-{3-[1,2-di(tert-butoxycarbonyl)-3-(3-methylbut-2-enyl)guanidino]propyl}-2,3,3a,4,5,9b-hexahydro-4-(3-hydroxypropyl)-1H-pyrrolo[3,2-c]quinoline-8-carboxylic acid
  参考文献：
  名称：

  An Asymmetric Total Synthesis of Martinellic Acid

  摘要：

  We describe an asymmetric total synthesis of the pyrrolo[3,2-c]quinoline natural product martinellic acid starting from pyrroglutamic acid. A convergent strategy involving a Pd-catalyzed aryl amination reaction of a chiral, non-racemic pyrrolidine derivative incorporates the C2-chiral center which controls the remaining two stereocenters. Elaboration of this adduct through a Grieco-elimination sets the stage for a diastereoselective intramolecular [3+2] azomethine ylide-alkene cycloaddition and the construction of the remaining two chiral centers. Elaboration of the cycloadduct and incorporation the prenyl guanidine units delivered martinellic acid after removal of the protecting groups.

  DOI：

  10.3987/com-16-s(s)81

文献信息

• Asymmetric total synthesis of martinelline and martinellic acid
  作者：Shuhei Ikeda、Masatoshi Shibuya、Yoshiharu Iwabuchi

  DOI：10.1039/b611121a

  日期：——

  Herein, we describe the first asymmetric total synthesis of (–)-martinelline ((–)-2) and the second total synthesis of (–)-martinellic acid ((–)-1) by employing a tandem Mukaiyama–Mannich reaction/aminal cyclization as the key step.

  在此，我们介绍了通过串联 Mukaiyama-Mannich 反应/氨基环化作为关键步骤，首次不对称全合成 (-)-martinelline ((-)-2)，以及第二次全合成 (-)-martinellic acid ((-)-1)。
• First Total Synthesis of Martinellic Acid, a Naturally Occurring Bradykinin Receptor Antagonist
  作者：Dawei Ma、Chengfeng Xia、Jiqing Jiang、Jianhua Zhang

  DOI：10.1021/ol016043h

  日期：2001.7.1

  [reaction: see text] The first total synthesis of martinellic acid, a naturally occurring bradykinin receptor antagonist, via a CuI-catalyzed coupling reaction of beta-amino ester 6 with 1,4-diiodobenzene and a guanylation reaction of secondary amine 3 under mild conditions as key steps, is described.

  [反应：参见正文]通过CuI催化的β-氨基酯6与1,4-二碘苯的偶联反应以及仲胺3的鸟嘌呤化反应，首次合成了天然的缓激肽受体拮抗剂马汀酸描述了作为关键步骤的条件。
• Total Synthesis of (−)-Martinellic Acid via Radical Addition−Cyclization−Elimination Reaction
  作者：Atsushi Shirai、Okiko Miyata、Norimitsu Tohnai、Mikiji Miyata、David J. Procter、David Sucunza、Takeaki Naito

  DOI：10.1021/jo800560p

  日期：2008.6.1

  The asymmetric total synthesis of martinellic acid, the first pyrrolo[3,2-c]quinoline alkaloid found in nature, is described. Three key steps in our synthesis of (−)-martinellic acid are the Bu3SnH-promoted radical addition−cyclization−elimination (RACE) reaction of an oxime ether with an α,β-unsaturated ester to generate the pyrrolo[3,2-c]quinoline core, a chemoselective lactam carbonyl reduction

  描述了天然存在的第一种吡咯并[3,2- c ]喹啉生物碱马汀酸的不对称全合成。我们合成（-）-马来酸的三个关键步骤是肟醚与α，β-不饱和酯的Bu 3 SnH促进的自由基加成-环化-消除（RACE）反应，生成吡咯并[3,2 - c ^ ]喹啉核，化学选择性内酰胺羰基还原，和胍基化Mitsunobu反应条件下进行。还使用SmI 2研究了关键的自由基环化反应。（-）-Martinellic acid由市售的4-溴-3-甲基苯甲酸甲酯以比以前的合成更少的步骤合成，并且总产率得到了提高。
• Aromatic Nucleophilic Substitution or CuI-Catalyzed Coupling Route to Martinellic Acid
  作者：Dawei Ma、Chengfeng Xia、Jiqing Jiang、Jianhua Zhang、Wenjun Tang

  DOI：10.1021/jo026125z

  日期：2003.1.1

  Condensation of beta-amino ester 8b with triflate 7 gives N-aryl amino ester 11, which is converted into 2-substituted 4-oxoquinoline 4 using an intramolecular Dieckmann reaction as the key step. CuI-mediated coupling of beta-amino ester 8a with 1,4-diiodobenzene followed by an intramolecular acylation and Pd-catalyzed carbonylation provide another manner to 4. Alkylation of 4 and subsequent reductive amination deliver the cyclic imine 14, which is transformed into triamine 3 by ordinary operations. Guanylation of 3 under mild condition followed by deprotection results in the synthesis of martinellic acid 1.
• An Asymmetric Total Synthesis of Martinellic Acid
  作者：Carl J. Lovely、Vivek Badarinarayana、Hossen Mahmud

  DOI：10.3987/com-16-s(s)81

  日期：——

  We describe an asymmetric total synthesis of the pyrrolo[3,2-c]quinoline natural product martinellic acid starting from pyrroglutamic acid. A convergent strategy involving a Pd-catalyzed aryl amination reaction of a chiral, non-racemic pyrrolidine derivative incorporates the C2-chiral center which controls the remaining two stereocenters. Elaboration of this adduct through a Grieco-elimination sets the stage for a diastereoselective intramolecular [3+2] azomethine ylide-alkene cycloaddition and the construction of the remaining two chiral centers. Elaboration of the cycloadduct and incorporation the prenyl guanidine units delivered martinellic acid after removal of the protecting groups.