Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, Saint Petersburg 199034, Russian Federation.
Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklaya St. 6, Moscow 117198, Russian Federation.
J Org Chem. 2022 Aug 5;87(15):10199-10207. doi: 10.1021/acs.joc.2c01141. Epub 2022 Jul 20.
Sulfonium and selenonium salts, represented by -aryl dibenzothiophenium and -aryl dibenzoselenophenium triflates, were found to exhibit remarkable catalytic activity in the model Groebke-Blackburn-Bienaymé reaction. Kinetic analysis and density functional theory (DFT) calculations indicated that their catalytic effect is induced by the ligation of the reaction substrates to the σ-holes on the S or Se atom of the cations. The experimental data indicated that although 10-fold excess of the chloride totally inhibits the catalytic activity of the sulfonium salts, the selenonium salt remains catalytically active, which can be explained by the experimentally found lower binding constant of the selenonium derivative to chloride in comparison with the sulfonium analogue. Both types of salts exhibit lower catalytic activity in the model reaction than dibenziodolium species.
砜盐和硒盐，以 -芳基二苯并噻吩𬭩和 -芳基二苯并硒吩𬭩三氟甲磺酸酯为代表，在 Groebke-Blackburn-Bienaymé 反应模型中表现出显著的催化活性。动力学分析和密度泛函理论（DFT）计算表明，它们的催化作用是由反应底物与阳离子的 S 或 Se 原子上的 σ 空穴的配位诱导的。实验数据表明，尽管 10 倍过量的氯化物完全抑制了砜盐的催化活性，但硒盐仍然具有催化活性，这可以用实验中发现的硒盐衍生物与氯化物的结合常数低于砜盐类似物来解释。这两种盐在模型反应中的催化活性均低于二苯并碘𬭩物种。
