Metal-catalyzed dealkoxylative C(aryl)-C(sp3) 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, alpha-CH active, and suitable for various further modifications.