Metal-catalyzed dealkoxylative C_aryl-C sp 3 cross-coupling - Replacement of aromatic methoxy groups of aryl ethers by employing a functionalized nucleophile

The direct replacement of aromatic methoxy groups with activated carbon nucleophiles would give rise to novel synthetic pathways for targeted and diversity-oriented syntheses. We demonstrate here that this transformation can be achieved in a one-step reaction involving a bifunctional organolithium nucleophile in combination with a C_Ar-OMe bond-cleaving nickel catalyst. The resulting products are stable, α-CH active, and suitable for various further modifications. The direct replacement of aromatic methoxy groups with activated carbon nucleophiles would give rise to novel synthetic pathways for targeted and diversity-oriented syntheses. The use of a bifunctional nucleophile in a nickel-catalyzed cross-coupling reaction has resulted in diverse aryl methyl ethers being transformed into α-carbon-activated products.