Diruthenium Catalysis Enables Base‐Free Directed C–H Acylation

Comprehensive Summary Dinuclear metal catalysis has garnered increasing attention due to its distinct advantages arising from synergistic substrate capture and indirect activation/regulation. Among these systems, diruthenium catalysts remain relatively underexplored and have primarily been applied in transformations such as oxidation, amination, cyclopropanation, and hetero‐Diels–Alder reactions. Building upon these advances, we report herein the first example of a diruthenium‐catalyzed N‐directed C–H acylation. This reaction proceeds efficiently under exogenous base‐free conditions, thereby overcoming the limitations of traditional methods that rely on stoichiometric bases, and exhibiting the notable advantage of wide substrate scope. Mechanistic studies confirm that the diruthenium framework exhibits higher catalytic activity compared to its mononuclear analogues. Furthermore, the reaction is readily scalable to gram‐scale, providing a mild and sustainable approach for the efficient construction of carbonyl‐containing heteroaromatic compounds. More importantly, the resulting carbonyl products serve as key synthetic intermediates that can be further transformed into high‐value functional molecules—including alcohols, amines, oximes, and complex heterocycles—through various derivatization transformations such as reduction, nucleophilic addition, condensation, and cross‐coupling reactions, fully demonstrating the synthetic utility and late‐stage derivatization potential of this methodology.