Post-coordination of Ru(ii) controlled regioselective B(4)-H acylmethylation of -carboranes with sulfoxonium ylides.

Despite significant progress in the B-H functionalization of carboranes, the development of cost-effective catalytic systems devoid of noble metals, coupled with mechanistic validation of regioselectivity control, remains a formidable challenge. Herein, we disclose an Ag salt-free, redox-neutral, and inexpensive ruthenium(ii)-catalyzed protocol that enables exclusive B(4)-H acylmethylation of -carboranes through a novel post-coordination strategy. By exploiting weakly coordinating carboxylic acid as a traceless directing group, this method achieves excellent mono-site selectivity for B-C(sp) bond formation using diverse sulfoxonium ylides, demonstrating both functional group tolerance and synthetic scalability. This work not only establishes a practical synthetic platform but also addresses critical mechanistic questions unresolved in prior analogous studies. Through deuterium labeling, high-resolution mass spectrometry (HRMS) tracking, and single-crystal X-ray analysis of critical Ru intermediates, we unequivocally demonstrate that the mono-site selectivity originates from a unique post-coordination mode of Ru(ii). The Ru catalyst simultaneously engages both the carboxylic acid and the enolizable acylmethyl moiety in the mono-acylated intermediate, thereby dictating the B(4)-H activation trajectory. Our findings establish a generalizable platform for regiocontrolled carborane functionalization while defining mechanistic paradigms in transition metal-mediated B-H activation chemistry.