Su Jingwen, Guo Wenbin, Liu Yi, Kong Lichun, Zheng Hanliang, Zhu Gangguo
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, P. R. China.
Chem Commun (Camb). 2023 Feb 9;59(13):1821-1824. doi: 10.1039/d2cc06068j.
A copper-catalyzed, redox-neutral cascade difluoroalkylation/5- annulation/β-fluorine cleavage of ynones is developed, providing a direct and stereoselective method to access synthetically important α-monofluoroalkenyl cyclopentanones. Mechanistic studies suggest an unprecedented Cu-assisted β-fluorine fragmentation, which may be valuable for the challenging but important C-F bond activation. Moreover, the generated difluorocarbene was found to serve as an effective reductant for the regeneration of copper(I) catalyst, thus avoiding the addition of external reductants.
开发了一种铜催化、氧化还原中性的炔酮级联二氟烷基化/5-环化/β-氟裂解反应，提供了一种直接且立体选择性的方法来合成具有重要合成价值的α-单氟烯基环戊酮。机理研究表明存在一种前所未有的铜辅助β-氟断裂，这对于具有挑战性但重要的C-F键活化可能具有重要价值。此外，发现生成的二氟卡宾可作为一种有效的还原剂用于再生铜（I）催化剂，从而避免添加外部还原剂。
