3,3'-dimethylene-1,1'-bisindoline | 1606129-93-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吲哚及其衍生物
• 英文名称: 3,3'-dimethylene-1,1'-bisindoline
• 英文别名: 3-methylidene-1-(3-methylidene-2H-indol-1-yl)-2H-indole
• CAS: 1606129-93-4
• 化学式: C₁₈H₁₆N₂
• 分子量: 260.338
• InChiKey: LYTCGFCVBACGIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3'-dimethylene-1,1'-bisindoline 在 D(+)-10-樟脑磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以100%的产率得到3,3'-dimethyl-1,1'-bisindole
  参考文献：
  名称：

  Towards a biomimetic synthesis of schischkiniin: assembling the bis-dihydropyrazinone cycloaddition precursor

  摘要：

  The final step in the biosynthesis of the natural product schischkiniin is proposed to be a photochemically driven [2+2]-cycloaddition between two dihydropyrazinone units tethered to a 1,1 '-bisindole. Herein, we describe the extensive efforts aimed at synthesizing the cycloaddition precursor 2, which has been obtained as its di-Boc protected derivative 30. Two bidirectional approaches were examined, both starting with the diallylated hydrazobenzene 19 undergoing two simultaneous intramolecular Heck cyclizations to give 3,3 '-dimethylene-1,1 '-bisindoline (20), which was readily converted to the 1,1 '-bisindole-3,3 '-dicarbaldehyde (14) by a bromination hydrolysis oxidation sequence. In the initial approach, the simultaneous addition of the pyrazinyl Grignard 15 to dicarbaldehyde 14 followed by reduction and demethylation was successful, but the imines in the resulting bis-pyrazinone 5 could not be selectively reduced to the cycloaddition precursor 2. A revised route involving simultaneous Horner-Wadsworth-Emmons reactions between dicarbaldehyde 14 and phosphonoglycine 23 followed by reduction gave 1,1 '-bistryptophan 25, which underwent two consecutive thermally driven amidations to the bisamide 27. Acid-mediated cyclization of 27 gave the di-Boc protected cycloaddition precursor 30, from which the Boc groups could not be removed under a variety of conditions. These results provide a platform for an eventual biomimetic synthesis of 1, as well as demonstrating that 1,1 '-bisindoles are sturdy heterocyclic motifs capable of surviving lengthy synthetic sequences. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.03.081
• 作为产物：
  描述：

  1,2-二烯丙基-1,2-双(2-碘苯基)肼 在 silver carbonate 、 palladium diacetate 、 三苯基膦 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 18.0h， 以73%的产率得到3,3'-dimethylene-1,1'-bisindoline
  参考文献：
  名称：

  Towards a biomimetic synthesis of schischkiniin: assembling the bis-dihydropyrazinone cycloaddition precursor

  摘要：

  The final step in the biosynthesis of the natural product schischkiniin is proposed to be a photochemically driven [2+2]-cycloaddition between two dihydropyrazinone units tethered to a 1,1 '-bisindole. Herein, we describe the extensive efforts aimed at synthesizing the cycloaddition precursor 2, which has been obtained as its di-Boc protected derivative 30. Two bidirectional approaches were examined, both starting with the diallylated hydrazobenzene 19 undergoing two simultaneous intramolecular Heck cyclizations to give 3,3 '-dimethylene-1,1 '-bisindoline (20), which was readily converted to the 1,1 '-bisindole-3,3 '-dicarbaldehyde (14) by a bromination hydrolysis oxidation sequence. In the initial approach, the simultaneous addition of the pyrazinyl Grignard 15 to dicarbaldehyde 14 followed by reduction and demethylation was successful, but the imines in the resulting bis-pyrazinone 5 could not be selectively reduced to the cycloaddition precursor 2. A revised route involving simultaneous Horner-Wadsworth-Emmons reactions between dicarbaldehyde 14 and phosphonoglycine 23 followed by reduction gave 1,1 '-bistryptophan 25, which underwent two consecutive thermally driven amidations to the bisamide 27. Acid-mediated cyclization of 27 gave the di-Boc protected cycloaddition precursor 30, from which the Boc groups could not be removed under a variety of conditions. These results provide a platform for an eventual biomimetic synthesis of 1, as well as demonstrating that 1,1 '-bisindoles are sturdy heterocyclic motifs capable of surviving lengthy synthetic sequences. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2014.03.081