3,3'-di(hydroxymethyl)-1,1'-bisindole

• 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'-di(hydroxymethyl)-1,1'-bisindole
• 英文别名: [1-[3-(Hydroxymethyl)indol-1-yl]indol-3-yl]methanol；[1-[3-(hydroxymethyl)indol-1-yl]indol-3-yl]methanol
• 化学式: C₁₈H₁₆N₂O₂
• 分子量: 292.337
• InChiKey: VKXRLYQGPVXPMD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  50.3
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3,3'-di(hydroxymethyl)-1,1'-bisindole 在 三乙基硅烷 、 manganese(IV) oxide 、 三甲基氯硅烷 、 三氟化硼乙醚 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 38.5h， 生成 3,3'-([1,1'-Bisindole]-3,3'-diylbis(methylene))bis(pyrazin-2-one)
  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 、 N-溴代丁二酰亚胺(NBS) 、 palladium diacetate 、 碳酸氢钠 、 三苯基膦 作用下， 以 四氢呋喃 、 N-甲基吡咯烷酮 、 氯仿 、 水 为溶剂， 反应 19.05h， 生成 3,3'-di(hydroxymethyl)-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

文献信息

• Oxidation chemistry of indole-3-methanol
  作者：Rajendra N. Goyal、Anil Kumar、Priyanka Gupta

  DOI：10.1039/b006855l

  日期：——

  The electrochemically driven and persulfate-mediated oxidations of indole-3-methanol have been studied in phosphate buffers. The electrochemical oxidation was carried out at a pyrolytic graphite electrode and the electrode reaction is found to follow the ECE mechanism. The kinetics of the UV-absorbing intermediate were followed spectrophotometrically and decay occurred in a pseudo-first-order reaction. On the other hand, the oxidation of indole-3-methanol by persulfate followed pseudo-first-order kinetics having first-order with respect to substrate. This reaction takes place with a second-order rate constant of (0.13 ± 0.005) dm3 mol−1 s−1. A detailed interpretation of the redox mechanism for indole-3-methanol in both the oxidations has been suggested.

  在磷酸盐缓冲液中研究了电化学驱动和过硫酸盐介导的吲哚-3-甲醇的氧化反应。电化学氧化在热解石墨电极上进行，发现电极反应遵循ECE机制。通过分光光度法跟踪了紫外吸收中间体的动力学，衰减过程呈现伪一级反应行为。另一方面，过硫酸盐对吲哚-3-甲醇的氧化反应遵循伪一级动力学，并且对底物呈一阶反应。该反应的二级反应速率常数为(0.13 ± 0.005) dm³ mol⁻¹ s⁻¹。提出了对吲哚-3-甲醇在这两种氧化反应中电氧化还原机制的详细解释。