Burykina Julia V, Kobelev Andrey D, Shlapakov Nikita S, Kostyukovich Alexander Yu, Fakhrutdinov Artem N, König Burkhard, Ananikov Valentine P
Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, Moscow, 119991, Russia.
Lomonosov Moscow State University, Leninskie Gory GSP-1, 1-3, Moscow, 119991, Russia.
Angew Chem Int Ed Engl. 2022 Apr 19;61(17):e202116888. doi: 10.1002/anie.202116888. Epub 2022 Mar 2.
The first example of an intermolecular thiol-yne-ene coupling reaction is reported for the one-pot construction of C-S and C-C bonds. Thiol-yne-ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via C-S three-electron σ-bond formation). Investigation of the reaction mechanism by combining online ESI-UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern-Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical-involving stages. As a result, previously unavailable products of the thiol-yne-ene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3-dienes.
报道了分子间硫醇-炔-烯偶联反应的首个实例，用于一锅法构建C-S键和C-C键。硫醇-炔-烯偶联为构建分子复杂性以获得高度官能化产物开辟了新的维度。曙红Y/DBU/甲醇光催化体系的使用抑制了氢原子转移（HAT）和缔合还原剂上转换（通过C-S三电子σ键形成）。通过结合在线ESI-UHRMS、EPR光谱、同位素标记、量子产率测定、循环伏安法、斯特恩-沃尔默测量和计算建模对反应机理进行研究，揭示了一个独特的光氧化还原循环，该循环具有四个涉及自由基的阶段。结果，以高选择性获得了高产率的硫醇-炔-烯反应先前无法得到的产物。它们可作为合成要求苛刻的活化1,3-二烯的稳定前体。
