Ruthenium-Catalyzed C(sp ² )–H Activation Using Pyridine and Imidazopyridine as Directing Groups for Selective Silylation

Ruthenium-catalyzed C(sp²)-H activation using pyridine and imidazopyridine directing groups enables direct ortho-silylation of 2-arylimidazoheterocycles with hydrosilanes as silylation reagents. This method achieves regioselective C(sp²)-H silylation without the need for preactivation, affording ortho-silylated arylimidazo[1,2-<i>a</i>]pyridines in high yields. Notably, this represents the first example of hydrosilane coupling with imidazo[1,2-<i>a</i>]pyridines via pentacyclometalated intermediates. The scalable protocol is compatible with a broad range of 2-aryl nitrogen-containing heterocycles. Experimental studies support the proposed catalytic cycle, and downstream derivatization reactions highlight the synthetic utility of the products. Furthermore, long-term cycling tests of NCM811||Li cells demonstrate that the silylated product, used as an electrolyte additive, significantly improves the cathode-electrolyte interfacial stability.