Wang Xiaohong, Zhang Xuemei, He Xiaochun, Guo Guangqing, Huang Qian, You Fengzhi, Wang Qingqing, Qu Ruiling, Zhou Fei, Lian Zhong
Department of Dermatology, State Key Laboratory of Biotherapy and Cancer Center, West China Hospital, Sichuan University, Chengdu, 610041, P.R. China.
Angew Chem Int Ed Engl. 2024 Dec 2;63(49):e202410334. doi: 10.1002/anie.202410334. Epub 2024 Oct 31.
The 1,2-hydroxysilylation of alkenes is crucial for synthesizing organosilicon compounds which are key intermediates in material science, pharmaceuticals, and organic synthesis. The development of strategies employing hydrogen atom transfer pathways is currently hindered by the existence of various competing reactions. Herein, we reported a novel mechanochemical strategy for the triphasic 1,2-hydroxysilylation of alkenes through a single-electron-transfer pathway. Our approach not only circumvents competitive reactions to enable the first-ever 1,2-hydroxysilylation of unactivated alkenes but also pioneers the research in mechanic force-induced triphasic reactions under ambient conditions. This gentle method offers excellent compatibility with various functional groups, operates under simple and solvent-free conditions, ensures rapid reaction time. Preliminary mechanistic investigations suggest that silylboronate can be transformed to a silicon radical by highly polarized LiTiO particles and oxygen under ball-milling condition.
烯烃的1,2-羟基硅基化反应对于合成有机硅化合物至关重要，这些化合物是材料科学、制药和有机合成中的关键中间体。目前，采用氢原子转移途径的策略发展受到各种竞争反应的阻碍。在此，我们报道了一种通过单电子转移途径实现烯烃三相1,2-羟基硅基化反应的新型机械化学策略。我们的方法不仅规避了竞争反应，实现了未活化烯烃的首例1,2-羟基硅基化反应，还开创了环境条件下机械力诱导三相反应的研究。这种温和的方法与各种官能团具有出色的兼容性，在简单且无溶剂的条件下操作，确保了快速的反应时间。初步机理研究表明，在球磨条件下，硅硼酸酯可通过高度极化的LiTiO颗粒和氧气转化为硅自由基。
