Robaszkiewicz Jakub, Chaładaj Wojciech, Pawluć Piotr, Zaranek Maciej
Center for Advanced Technologies, Adam Mickiewicz University, Uniwersytetu Poznańskiego 10, Poznań, 61-614, Poland.
Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, Poznań, 61-614, Poland.
Sci Rep. 2025 Jul 23;15(1):26809. doi: 10.1038/s41598-025-10180-1.
The diarylmethane backbone is a base of molecules relevant for various industrial and especially pharmaceutical applications where they serve as a platform for the discovery of new drugs. One of the most versatile methods of their synthesis are cross-coupling reactions that have served synthetic chemistry for nearly five decades and offer diverse opportunities for the synthesis of complex organic compounds. Although palladium catalysts have traditionally dominated this field, the emergence of first-row transition-metal (pre)catalysts presents promising alternatives because of their cost-effectiveness and the possibility of new reactivities. In this context, Negishi cross-coupling of benzylzinc bromide and its congeners with aryl, alkyl, alkenyl, alkynyl iodides and bromides, facilitated by simple cobalt halides without the addition of an auxiliary ligand, is presented. The optimisation of reaction conditions, including solvent selection, is discussed alongside the mechanistic insights gained through computational studies. A variety of diarylmethanes were synthesised under mild conditions, with yields comparable to those obtained with Pd catalysts, with excellent selectivity (> 99%) provided by commercially available anhydrous CoBr / DMAc catalytic system.
二芳基甲烷骨架是与各种工业应用特别是制药应用相关的分子基础，在这些应用中它们作为新药发现的平台。其合成方法中最通用的方法之一是交叉偶联反应，这种反应已为合成化学服务了近五十年，并为复杂有机化合物的合成提供了多种机会。尽管钯催化剂传统上在该领域占据主导地位，但第一排过渡金属（预）催化剂的出现因其成本效益和新反应性的可能性而呈现出有前景的替代方案。在此背景下，本文介绍了在不添加辅助配体的情况下，由简单的钴卤化物促进的苄基溴化锌及其同系物与芳基、烷基、烯基、炔基碘化物和溴化物的Negishi交叉偶联反应。同时讨论了反应条件的优化，包括溶剂选择，以及通过计算研究获得的机理见解。在温和条件下合成了多种二芳基甲烷，产率与使用钯催化剂获得的产率相当，市售无水CoBr₂ / DMAc催化体系提供了优异的选择性（> 99%）。
