1,2-二烯丙基-1,2-双(2-碘苯基)肼 | 1431934-72-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 1,2-二烯丙基-1,2-双(2-碘苯基)肼
• 英文名称: 1,2-diallyl-1,2-bis(2-iodophenyl)hydrazine
• 英文别名: 1,2-Bis(2-iodophenyl)-1,2-bis(prop-2-enyl)hydrazine；1,2-bis(2-iodophenyl)-1,2-bis(prop-2-enyl)hydrazine
• CAS: 1431934-72-3
• 化学式: C₁₈H₁₈I₂N₂
• 分子量: 516.163
• InChiKey: XIGIHQRHIQABOD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.6
• 重原子数：
  22
• 可旋转键数：
  7
• 环数：
  2.0
• 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：

  1,2-二烯丙基-1,2-双(2-碘苯基)肼 在 manganese(IV) oxide 、 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 、 二氯甲烷 、 氯仿 、 水 为溶剂， 反应 35.05h， 生成 1,1'-bisindole-3,3'-dicarbaldehyde
  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：

  2,2'-Diiodhydrazobenzol 在 potassium hydroxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 0.42h， 生成 1,2-二烯丙基-1,2-双(2-碘苯基)肼
  参考文献：
  名称：

  Schischkiniin support studies: synthetic access to 1,1′-bisindoles

  摘要：

  本文介绍了 1,1â²-双吲哚的第一种通用合成方法。利用两个同时进行的常温莫里班（MoriâBan）反应，对几种二烯丙基肼苯进行了双吲哚化，并将 N-N 键的裂解程度降到了最低。

  DOI：

  10.1039/c2cc37241j

文献信息

• Schischkiniin support studies: synthetic access to 1,1′-bisindoles
  作者：Christy Wang、Jonathan Sperry

  DOI：10.1039/c2cc37241j

  日期：——

  The first general synthetic approach to 1,1′-bisindoles is described. Two simultaneous, ambient temperature Mori–Ban reactions were used to effect bisindolization of several diallylated hydrazobenzenes with minimal cleavage of the N–N bond.

  本文介绍了 1,1â²-双吲哚的第一种通用合成方法。利用两个同时进行的常温莫里班（MoriâBan）反应，对几种二烯丙基肼苯进行了双吲哚化，并将 N-N 键的裂解程度降到了最低。
• Towards a biomimetic synthesis of schischkiniin: assembling the bis-dihydropyrazinone cycloaddition precursor
  作者：Christy Wang、Jonathan Sperry

  DOI：10.1016/j.tet.2014.03.081

  日期：2014.5

  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.