Ti-Promoted Pd- and Fe-Catalyzed Regiodivergent C–H Arylation of Pyridines

We report a practical, regiodivergent C-H arylation of pyridines. In the presence of Ti-1·2(TMPMgCl·LiCl), diverse 2- or 3-substituted pyridines undergo Pd-catalyzed C6-H arylation under mild conditions, overriding the classical <i>ortho</i>-directing effects. In contrast, Ti/Fe synergy delivers <i>ortho</i>-arylation for 3-substituted pyridines and <i>meta</i>-arylation for 2-substituted pyridines. This complementary strategy provides streamlined access to valuable 2,6-, 2,5-, and 2,3-difunctionalized pyridines from simple precursors and enables late-stage diversification of natural products and fungicides.