清华大学焦雷团队报道了双配体激活Pd催化碘芳烃的正烷基化反应。相关研究成果发表在2024年9月5日出版的《美国化学会杂志》。

由简单前体合成复杂的多取代芳香分子是有机化学的核心目标。

该文中，研究人员开发了一种利用双配体催化体系进行碘芳烃邻位烷基化的方法。通过将Pd/烯烃配体协同催化与大体积三烷基膦配体促进的C（sp2）-I还原消除相结合，建立了以芳基碘键重构为最后一步的邻位烷基化Catellani型反应，这为Catellani类反应开辟了新的合成机会。

通过深入的机理研究，研究人员分离并表征了关键的有机钯中间体，揭示了双配体在将Catellani型过程与C（sp2）-I还原消除相结合时的协同作用。

该研究展示了Pd/烯烃配体催化的独特优势，并强调了双配体体系在拓展Catellani化学空间方面的有效性。

附：英文原文

Title: Dual Ligand Enabled Pd-Catalyzed Ortho-Alkylation of Iodoarenes

Author: Xiao-Xia Wang, Lei Jiao

Issue&Volume: September 5, 2024

Abstract: The synthesis of complex polysubstituted aromatic molecules from simple precursors is a central goal in organic chemistry. In this study, we developed an approach for the ortho-alkylation of iodoarenes utilizing a dual ligand catalytic system. By combining Pd/olefin ligand cooperative catalysis with bulky trialkylphosphine ligand-promoted C(sp2)–I reductive elimination, we have established an ortho-alkylative Catellani-type reaction with the aryl-iodine bond reconstruction as the final step, which opens new synthetic opportunities within the Catellani-type reactions. Through in-depth mechanistic investigations, we have isolated and characterized key organopalladium intermediates, revealing the synergistic interaction of the dual ligands in merging the Catellani-type process with C(sp2)–I reductive elimination. The present study showcases the unique advantages of Pd/olefin ligand catalysis and emphasizes the effectiveness of the dual ligand system in expanding the chemical space of the Catellani chemistry.

DOI: 10.1021/jacs.4c06544

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c06544