Stang Martin, Hanada Erin M, Blum Suzanne A
Department of Chemistry, University of California, Irvine, California 92697-2025, United States.
J Org Chem. 2025 Jan 17;90(2):939-948. doi: 10.1021/acs.joc.4c02726. Epub 2025 Jan 2.
Activating agents enable the efficient preparation of organozinc complexes from zinc metal and organohalides, but their mechanisms had been obscured by the heterogeneous nature of these systems. Fluorescence microscopy, with the sensitivity to detect surface reaction intermediates, reveals distinct activating mechanisms of widely used activation strategies: trimethylsilyl chloride, LiCl, DMSO, and Rieke zinc powder. The resulting development of mechanistic models provides a better understanding of the oxidative-addition-solubilization sequence in organozinc reagent formation and contains lessons for methods development.
活化剂能够使锌金属与有机卤化物高效制备有机锌配合物，但其作用机制因这些体系的多相性质而变得模糊不清。荧光显微镜具有检测表面反应中间体的灵敏度，揭示了广泛使用的活化策略（三甲基氯硅烷、LiCl、二甲基亚砜和雷克锌粉）的独特活化机制。由此产生的机理模型的发展有助于更好地理解有机锌试剂形成过程中的氧化加成-增溶序列，并为方法开发提供了经验教训。
