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Alumination of aryl methyl ethers: switching between sp2 and sp3 C-O bond functionalisation with Pd-catalysis.

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.

SUBMITTER: Brown RK

PROVIDER: S-EPMC8567294 | biostudies-literature | 2021 Nov

REPOSITORIES: biostudies-literature

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Alumination of aryl methyl ethers: switching between sp2 and sp3 C-O bond functionalisation with Pd-catalysis.

Brown Ryan K RK Hooper Thomas N TN Rekhroukh Feriel F White Andrew J P AJP Costa Paulo J PJ Crimmin Mark R MR

Chemical communications (Cambridge, England) 20211104 88

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 sp<s ...[more]

PMID: 34672313

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