Alumination of Aryl Methyl Ethers: Switching Between Sp2 and Sp3 C–O Bond Functionalisation with Pd-Catalysis

The reaction of [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl, 1) with aryl methyl ethers proceeded with alumination of the sp3 C–O bond by a presumed SN2 pathway. The selectivity of this reaction could be switched by inclusion of a catalyst. In the presence of [Pd(PCy3)2], chemoselective sp2 C–O bond functionalisation was observed. Kinetic isotope experiments and DFT calculations support a catalytic pathway involving the ligand-assisted oxidative addition of the sp2 C–O bond to a Pd---Al intermetallic complex. The net result of both non-catalysed and catalytic pathways is the generation of polar organoaluminium complexes from aryl methyl ethers with complete atom-efficiency. Switches in selectivity yield isomeric products from a single starting material. The methodology (and mechanistic insight) holds promise as a means to functionalise aromatic molecules derived from lignin depolymerisation and we demonstrate an application to a derivative of vanillin.