Copper-Catalyzed Carbonylative Cross-Coupling of Alkyl Iodides and Amines

A general copper-catalyzed carbonylative cross-coupling between amines and alkyl iodides is reported. Using a simple combination of catalytic amounts of copper(I) chloride and N,N,N',N",N"-pentamethyldiethylenetriamine in the presence of sodium hydroxide under carbon monoxide pressure, a broad range of alkyl iodides and amines can be efficiently coupled to the corresponding amides that are obtained in good to excellent yields. Notable features of this process - the first one relying on a base metal catalyst - include the availability and low cost of the catalytic system, its successful use with primary, secondary, tertiary alkyl iodides and all classes of amines - with no or limited competing nucleophilic substitution without CO incorporation - as well as its efficiency with complex alkyl iodides and amines. Mechanistic studies demonstrated that a radical pathway is operative and the key role of CO.