Metal-Catalyzed Dealkoxylative CarylC sp 3 Cross-Coupling-Replacement of Aromatic Methoxy Groups of Aryl Ethers by Employing a Functionalized Nucleophile

• Published in: Angewandte Chemie International Edition Vol. 53; no. 47; pp. 12912 - 12915
• Main Authors: Leiendecker, Matthias, Hsiao, Chien-Chi, Guo, Lin, Alandini, Nurtalya, Rueping, Magnus
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 17.11.2014; WILEY‐VCH Verlag
• Subjects: aryl ethers; cross-coupling; CO bond cleavage; methoxy functionalization; nickel
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201402922

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 CAr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.