Metal-catalyzed dealkoxylative C(aryl)-C(sp3) cross-coupling-replacement of aromatic methoxy groups of aryl ethers by employing a functionalized nucleophile

Matthias Leiendecker; Chien-Chi Hsiao; Lin Guo; Nurtalya Alandini; Magnus Rueping

doi:10.1002/anie.201402922

Metal-catalyzed dealkoxylative C(aryl)-C(sp3) cross-coupling-replacement of aromatic methoxy groups of aryl ethers by employing a functionalized nucleophile

Angew Chem Int Ed Engl. 2014 Nov 17;53(47):12912-5. doi: 10.1002/anie.201402922. Epub 2014 Sep 22.

Authors

Matthias Leiendecker¹, Chien-Chi Hsiao, Lin Guo, Nurtalya Alandini, Magnus Rueping

Affiliation

¹ Institut für Organische Chemie, RWTH Aachen University, Landoltweg 1, 52074 Aachen (Germany).

PMID: 25250516
DOI: 10.1002/anie.201402922

Abstract

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.

Keywords: CO bond cleavage; aryl ethers; cross-coupling; methoxy functionalization; nickel.