Li Long-Hai, Wei Hao-Zhao, Wei Yin, Shi Min
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Science, Chinese Academy of Sciences 345 Lingling Road Shanghai 200032 China
Key Laboratory for Advanced Materials, Institute of Fine Chemicals, School of Chemistry & Molecular Engineering, East China University of Science and Technology 130 Meilong Road Shanghai 200237 China.
Chem Sci. 2022 Jan 5;13(5):1478-1483. doi: 10.1039/d1sc06784b. eCollection 2022 Feb 2.
A strategy for overcoming the limitation of the Morita-Baylis-Hillman (MBH) reaction, which is only applicable to electron-deficient olefins, has been achieved visible-light induced photoredox catalysis in this report. A series of non-electron-deficient olefins underwent the MBH reaction smoothly a novel photoredox-quinuclidine dual catalysis. The formed key β-quinuclidinium radical intermediates, derived from the addition of olefins with quinuclidinium radical cations, are used to enable the MBH reaction of non-electron-deficient olefins. On the basis of previous reports, a plausible mechanism is suggested. Mechanistic studies, such as radical probe experiments and density functional theory (DFT) calculations, were also conducted to support our proposed reaction pathways.
本报告中，通过可见光诱导的光氧化还原催化作用，实现了一种克服仅适用于缺电子烯烃的森田-贝利斯-希尔曼（MBH）反应局限性的策略。一系列非缺电子烯烃通过新型光氧化还原-奎宁环双重催化顺利进行了MBH反应。由烯烃与奎宁环阳离子加成形成的关键β-奎宁环鎓自由基中间体，用于实现非缺电子烯烃的MBH反应。基于先前的报道，提出了一种合理的机理。还进行了自由基探针实验和密度泛函理论（DFT）计算等机理研究，以支持我们提出的反应途径。
