Remote meta-C-H Olefination of α-Hydroxyacetophenones via a Microwave-Assisted Palladium-Catalyzed Template Strategy.

α-Hydroxyacetophenones represent important structural motifs in pharmaceuticals and functional molecules; however, their selective remote functionalization remains challenging due to the cooperative ortho-directing effects of the ketone and hydroxyl groups. Herein, we report a palladium-catalyzed, simple aliphatic nitrile template-assisted selective meta-C-H olefination of α-hydroxyacetophenones under microwave-accelerated conditions. The designed directing template overrides the intrinsic proximal bias, enabling efficient, highly regioselective meta-functionalization with broad substrate scope and applicability for drug diversification. The template can be selectively removed under mild conditions to afford free α-hydroxy ketones, which can then be further transformed into 1,2-dicarbonyl compounds.