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Alumination of aryl methyl ethers: switching between sp2 and sp3 C-O bond functionalisation with Pd-catalysis
Ryan K Brown1, Thomas N Hooper1, Feriel Rekhroukh2
1Department of Chemistry, Molecular Sciences Research Hub, Imperial College London, 82 Wood Lane, Shepherds Bush, London, W12 0BZ, UK. m.crimmin@imperial.ac.uk.
Abstract:
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.
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