Schmidt Elena Yu, Tatarinova Inna V, Lobanova Natal'ya A, Ushakov Igor A, Bagryanskaya Irina Yu, Trofimov Boris A
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia.
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Novosibirsk 630090, Russia.
Org Biomol Chem. 2023 Sep 13;21(35):7209-7218. doi: 10.1039/d3ob01311a.
We have discovered that three molecules of arylacetylene are rapidly (15 min) assembled with one molecule of nitrile at room temperature in the KOBu/DMSO system to afford 2-aryl-3-arylethynyl-4-aryl-5-benzyl-1-pyrroles in up to 76% yield. We assume that this unprecedented self-organization process involves the cascade addition of acetylenic carbanions, first to the CN, then to the CC and CC bonds of the intermediates, followed by pyrrole ring closure the intramolecular nucleophilic addition of the NH functional group to the CC bond of the final intermediates.
我们发现，在室温下的KOBu/DMSO体系中，三分子芳基乙炔与一分子腈迅速（15分钟）组装，以高达76%的产率得到2-芳基-3-芳基乙炔基-4-芳基-5-苄基-1-吡咯。我们推测，这一前所未有的自组装过程涉及炔基碳负离子的级联加成，首先加成到C≡N上，然后加成到中间体的C=C和C-C键上，接着是吡咯环闭合——NH官能团对最终中间体的C=C键进行分子内亲核加成。
