Tian Ya-Ming, Hofmann Evamaria, Silva Wagner, Pu Xiang, Touraud Didier, Gschwind Ruth M, Kunz Werner, König Burkhard
Faculty of Chemistry and Pharmacy, Institute of Organic Chemistry, University Regensburg, 93040, Regensburg, Germany.
Faculty of Chemistry and Pharmacy, Institute of Physical and Theoretical Chemistry, University Regensburg, 93040, Regensburg, Germany.
Angew Chem Int Ed Engl. 2023 Apr 17;62(17):e202218775. doi: 10.1002/anie.202218775. Epub 2023 Mar 8.
The amino alcohol meglumine solubilizes organic compounds in water and enforces the formation of electron donor acceptor (EDA) complexes of haloarenes with indoles, anilines, anisoles or thiols, which are not observed in organic solvents. UV-A photoinduced electron transfer within the EDA complexes induces the mesolytic cleavage of the halide ion and radical recombination of the arenes leading, after rearomatization and proton loss to C-C or C-S coupling products. Depending on the substitution pattern selective and unique cross-couplings are observed. UV and NMR measurements reveal the importance of the assembly for the photoinduced reaction. Enforced EDA aggregate formation in water allows new activation modes for organic photochemical synthesis.
氨基醇葡甲胺可使有机化合物在水中溶解，并促使卤代芳烃与吲哚、苯胺、苯甲醚或硫醇形成电子供体-受体（EDA）络合物，而在有机溶剂中则不会形成这种络合物。EDA络合物内的紫外-A光诱导电子转移会引发卤离子的均裂裂解以及芳烃的自由基重组，经过再芳构化和质子损失后，生成碳-碳或碳-硫偶联产物。根据取代模式，可以观察到选择性且独特的交叉偶联反应。紫外和核磁共振测量结果揭示了该组装体对光诱导反应的重要性。在水中强制形成EDA聚集体为有机光化学合成提供了新的活化模式。
