Alumination of aryl methyl ethers: switching between sp2 and sp3 C-O bond functionalisation with Pd-catalysis.
Ryan K BrownThomas N HooperFeriel RekhroukhAndrew J P WhitePaulo J CostaMark R CrimminPublished in: Chemical communications (Cambridge, England) (2021)
The reaction of [{(ArNCMe)2CH}Al] (Ar = 2,6-di-iso-propylphenyl) with aryl methyl ethers proceeded with alumination of the sp3 C-O bond. 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.