Cu/Ru Sequential Catalysis via In Situ Directing Group Formation for Site‐Selective CH Arylation

A Cu/Ru bimetallic sequential catalytic strategy combining copper‐catalyzed azide‐alkyne cycloaddition (CuAAC) with Ru‐catalyzed CH activation is developed, enabling the in situ formation of nitrogen‐containing triazoles and their ortho CH arylation in a one‐pot dual‐functional transformation. This system innovatively employs the 1,2,3‐triazole formed via CuAAC as an endogenous directing group, facilitating sequential [3+2] cycloaddition and Ru‐mediated CH functionalization through a stepwise catalytic approach. The strategy overcomes the limitations of traditional preactivation and exhibits excellent regioselectivity and broad substrate compatibility. This approach has been successfully applied to the late‐stage modification of pharmaceutical molecules, offering a new paradigm for the modular synthesis of complex compounds.