Zhu Hui-Min, Lei Tong, Liao Zhi-Xin, Xiang Jia-Chen, Wu An-Xin
School of Chemistry and Chemical Engineering, Southeast University, Nanjing, 211189, PR China.
State Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan, 430079, PR China.
Commun Chem. 2025 May 15;8(1):152. doi: 10.1038/s42004-025-01528-9.
Rearrangement reactions are generally considered to be a rapid and synergistic intramolecular reconstructing process that is insensitive to intermolecular intruders. We report that α-iminol rearrangements could be strategically redirected by the interception of Petasis reactions, in the context of being avoided by strong electron-withdrawing groups on the migrative aryl units. 1,4-Aryl migration prevails over 1,2-aryl migration via forming a boron-ate complex. By leveraging this reactivity, we developed a regiospecific synthesis of unsymmetrically 2,3-diaryl substituted indoles from three readily available feedstocks: an amine, an arylglyoxal, and a boronic acid. While traditional Petasis reactions with similar three-component inputs are typically applied to build C(sp)-C(sp) and C(sp)-C(sp) bonds, the present transformation offers a special opportunity for constructing a C(sp)-C(sp) linkage. Highly substituted indole motifs with structural diversity in the C2 position are easily accessed by this three-component reaction. A mechanism containing a copper-cobalt collaborative promotion process was suggested.
重排反应通常被认为是一种快速且协同的分子内重构过程，对分子间干扰不敏感。我们报道，在迁移芳基单元上的强吸电子基团避免α-亚胺醇重排的情况下，Petasis反应的截获可策略性地改变α-亚胺醇重排的方向。通过形成硼酸酯络合物，1,4-芳基迁移比1,2-芳基迁移更占优势。利用这种反应活性，我们从三种易得的原料：胺、芳基乙二醛和硼酸，开发了一种区域特异性合成不对称2,3-二芳基取代吲哚的方法。虽然具有类似三组分输入的传统Petasis反应通常用于构建C(sp)-C(sp)和C(sp)-C(sp)键，但目前的转化为构建C(sp)-C(sp)键提供了一个特殊的机会。通过这种三组分反应可以轻松获得在C2位置具有结构多样性的高度取代吲哚基序。提出了一种包含铜-钴协同促进过程的机理。
