A concurrent tandem catalytic (CTC) methodology has been developed for the hydrodehalogenation and the cyanation of aryl halides using a multifunctional copper catalyst. The tandem catalytic cycle consists of an initial halogen exchange step to form aryl iodides from less reactive aryl bromide and aryl chloride substrates. As the aryl iodide intermediate is generated, it is consumed as the substrate in a hydrodehalogenation or cyanation reaction. Aryl bromides and aryl chlorides were hydrodehalogenated in 12-87% yield using 20 mol% CuI, 1.5 eq. N,N'-dimethylcyclohexane-1,2-diamine ligand, and 2 eq. NaI in acetonitrile at 200 �C after 1-2 hours. Substrates with oxygen- or nitrogen-containing functional groups had substantially lower yields than hydrocarbon substrates. Aryl chlorides with a variety of electronic and steric properties underwent cyanation in yields up to 95% using 20 mol% CuI, 40 mol% N,N'-dimethylcyclohexane-1,2-diamine ligand, and 1.2 eq. KCN in acetonitrile at 200 �C in 1-2 hours. Evidence that hydrodehalogenation and cyanation are occurring via a CTC mechanism will be discussed.                                                   

Microwave-assisted copper-catalyzed reactions of aryl halides via concurrent tandem catalysis

245th National Meeting (2013)

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