Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h–1 was attained using an alkyl iodide. Side reactions of this catalytic system, ie, reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, ...