Liu Zhiqiang, Kole Goutam Kumar, Budiman Yudha P, Tian Ya-Ming, Friedrich Alexandra, Luo Xiaoling, Westcott Stephen A, Radius Udo, Marder Todd B
Institute of Inorganic Chemistry and Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Department of Chemistry, College of Engineering and Technology, SRM Institute of Science and Technology, SRM Nagar, Kattankulathur, Tamil Nadu, 603203, India.
Angew Chem Int Ed Engl. 2021 Jul 19;60(30):16529-16538. doi: 10.1002/anie.202103686. Epub 2021 Jun 17.
A novel protocol for the transition metal-free 1,2-addition of polyfluoroaryl boronate esters to aldehydes and ketones is reported, which provides secondary alcohols, tertiary alcohols, and ketones. Control experiments and DFT calculations indicate that both the ortho-F substituents on the polyfluorophenyl boronates and the counterion K in the carbonate base are critical. The distinguishing features of this procedure include the employment of commercially available starting materials and the broad scope of the reaction with a wide variety of carbonyl compounds giving moderate to excellent yields. Intriguing structural features involving O-H⋅⋅⋅O and O-H⋅⋅⋅N hydrogen bonding, as well as arene-perfluoroarene interactions, in this series of racemic polyfluoroaryl carbinols have also been addressed.
报道了一种用于将多氟芳基硼酸酯无过渡金属地1,2-加成到醛和酮上的新方法，该方法可提供仲醇、叔醇和酮。对照实验和密度泛函理论计算表明，多氟苯基硼酸酯上的邻位氟取代基和碳酸盐碱中的抗衡离子K都是至关重要的。该方法的显著特点包括使用市售起始原料，以及该反应对多种羰基化合物具有广泛的适用范围，能给出中等至优异的产率。在这一系列外消旋多氟芳基甲醇中，还探讨了涉及O-H⋅⋅⋅O和O-H⋅⋅⋅N氢键以及芳烃-全氟芳烃相互作用的有趣结构特征。
