Aryl ether bond activation is of interest in the context of lignin conversion and organic methodology. To gain mechanistic insight, the intramolecular reactivity of group 9 and 10 metals supported by a terphenyl diphosphine bearing an aryl methyl ether was investigated. Ni0 and RhI were observed to activate aryl ether C-O bonds selectivity via oxidative addition. Non-selective activation of aryl and alkyl C-O bonds was observed at IrI. At Pd0 and Pt0, alkyl C-O bond activation was observed through oxidative addition. With group 10 MII halides, alkyl C-O bond activation was observed through Lewis-acid mediated alkyl halide elimination. Various modes of p-backbonding interactions between the central arene and the metal center were observed and these were correlated with trends in bond activation. Mechanistic details will be discussed.

Mechanistic studies of intramolecular aryl ether carbon-oxygen bond activation by group 9 and 10 transition metal centers

248th National Meeting (2014)

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