无催化剂合成巨型三（杂芳基）甲烷：新型药效基团三联体的合成及空间拥挤的三（杂芳基/芳基）甲基阳离子盐模型
Catalyst-free assembly of giant tris(heteroaryl)methanes: synthesis of novel pharmacophoric triads and model sterically crowded tris(heteroaryl/aryl)methyl cation salts.
作者信息
Abonia Rodrigo, Gutiérrez Luisa F, Insuasty Braulio, Quiroga Jairo, Laali Kenneth K, Zhao Chunqing, Borosky Gabriela L, Horwitz Samantha M, Bunge Scott D
机构信息
Research Group of Heterocyclic Compounds (GICH), Department of Chemistry, Universidad del Valle, A. A. 25360, Cali, Colombia.
Department of Chemistry, University of North Florida, 1 UNF Drive, Jacksonville, FL 32224, USA.
出版信息
Beilstein J Org Chem. 2019 Mar 12;15:642-654. doi: 10.3762/bjoc.15.60. eCollection 2019.
A series of giant tris(heteroaryl)methanes are easily assembled by one-pot three-component synthesis by simple reflux in ethanol without catalyst or additives. Diversely substituted indoles (Ar) react with quinoline aldehydes, quinolone aldehydes, chromone aldehydes, and fluorene aldehydes (ArCHO) and coumarins (Ar) in 1:1:1 ratio to form the corresponding tris(heteroaryl)methanes (ArArAr)CH along with (ArArAr)CH triads. A series of new 2:1 triads were also synthesized by coupling substituted indoles with ArCHO. The coupling reactions could also be carried out in water (at circa 80 °C) but with chemoselectivity favoring (ArArAr)CH over (ArArAr)CH. The molecular structure of a representative (ArArAr)CH triad was confirmed by X-ray analysis. Model tris(heteroaryl/aryl)methylium salts were generated by reaction with DDQ/HPF and studied by NMR and by DFT and GIAO-DFT.
通过在乙醇中简单回流，无需催化剂或添加剂，采用一锅三组分合成法可轻松组装出一系列巨型三（杂芳基）甲烷。不同取代的吲哚（Ar）与喹啉醛、喹诺酮醛、色酮醛和芴醛（ArCHO）以及香豆素（Ar）以1:1:1的比例反应，生成相应的三（杂芳基）甲烷（ArArAr）CH以及（ArArAr）CH三联体。通过将取代吲哚与ArCHO偶联，还合成了一系列新的2:1三联体。偶联反应也可在水中（约80°C）进行，但化学选择性有利于生成（ArArAr）CH而非（ArArAr）CH。通过X射线分析确定了代表性（ArArAr）CH三联体的分子结构。通过与DDQ/HPF反应生成模型三（杂芳基/芳基）甲基盐，并通过核磁共振、密度泛函理论和GIAO - DFT进行研究。
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