Bidusenko Ivan A, Schmidt Elena Yu, Ushakov Igor A, Vashchenko Alexander V, Protsuk Nadezhda I, Orel Vladimir B, Vitkovskaya Nadezhda M, Trofimov Boris A
E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences, 1 Favorsky Str., 664033 Irkutsk, Russia.
Laboratory of Quantum-Chemical Modeling of Molecular Systems, Irkutsk State University, 1 K. Marx Street, 664003 Irkutsk, Russia.
J Org Chem. 2022 Sep 16;87(18):12225-12239. doi: 10.1021/acs.joc.2c01372. Epub 2022 Aug 31.
Semistabilized diazatrienyl anions are generated by the reaction of 2-pyridylarylimines with arylacetylenes in superbase systems MOBu (M = Li, Na, K)/DMSO at ambient temperature for 15 min. The initial intermediate -centered propargyl-1,3-diaza-1,3,5-trienyl anions undergo intermolecular cyclization to benzyl imidazopyridine anions (formally [3 + 2] cycloaddition), further intercepting a second molecule of the starting pyridylimines or a proton of medium to afford ()-stilbene/imidazopyridine ensembles and benzyl imidazopyridines. The charge distribution in all intermediate anions and their synthetic evolution are consistent with quantum-chemical analysis (B2PLYPD/6-311+G**//B3LYP/6-31+G*).
在超碱体系MOBu（M = Li、Na、K）/DMSO中，于室温下反应15分钟，2-吡啶基芳基亚胺与芳基乙炔反应生成半稳定的重氮三烯基阴离子。最初以中间体为中心的炔丙基-1,3-二氮杂-1,3,5-三烯基阴离子发生分子内环化生成苄基咪唑并吡啶阴离子（形式上为[3 + 2]环加成），进一步截获一分子起始吡啶基亚胺或介质中的一个质子，得到（）-芪/咪唑并吡啶组合体和苄基咪唑并吡啶。所有中间体阴离子中的电荷分布及其合成演变与量子化学分析（B2PLYPD/6-311+G**//B3LYP/6-31+G*）一致。
