A novel, highly versatile and efficient method has been developed for the Barbier–Grignard‐type arylation of ketones and an unexpected cross‐coupling of phenolic ketones was observed using unactivated bromides and magnesium in tetrahydrofuran/toluene at 96 °C promoted by multicatalysts of cupric bromide (15 mol%), bismuth chloride (5 mol%) and silver bromide (10 mol%). The substituent and electronic effects on the reaction have been discussed. High yields of arylation and cross‐coupling have been attained under mild conditions. A novel reasonable mechanism involving a quinone intermediate is proposed. The high chemical selectivity in the cross‐coupling to the hydroxy group of phenolic ketones should help ketones find new applications.magnified image
The Barbier—Grignard reaction of aryl bromides with cyclohexanone (I) and various alkyl and/or aryl ketones (IV) is achieved in the presence of a three‐component catalyst mixture.
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