The efficient development of new medicines that treat and prevent diseases plays a vital role to improve the quality of human life. Seminal work by Lovering has shown that increasing fraction of sp 3 hybridized carbons correlates with the clinical success of drug candidates. Therefore, the selective construction of sp 3 -enriched centers is among the most important reactions. In the arsenal of organic chemists, transition metalcatalyzed cross-coupling of unactivated alkyl halides with organometallic reagents remains one of the most straightforward and modular approaches to the connection of sp 3 -hybridized carbons. Tremendous progress has been made in this area through the use of palladium, and, more recently, nickel catalysts. On the other hand, copper catalysts represent appealing alternatives to their palladium and nickel counterparts. As copper is one of the most abundant transition metals in Earth's crust, it is much less expensive and more globally available than Pd and Ni [e.g., Cu(OAc)2 < $1/g, Ni(OAc)2 ca. $10/g, and Pd(OAc)2 ca. $80/g]. In addition, being an essential trace element vital to the health of humans and other living organisms, copper salts typically have low toxicity and little environmental impact, as indicated by the higher permitted daily exposure values (Cu 3400 µg, Ni 220 µg, and Pd 100 µg). Despite these prominent economic and environmental features, the engagement of unactivated haloalkanes in coppercatalyzed cross-coupling reactions remains challenging. The main difficulty associated with such processes has been attributed to the sluggish two-electron oxidative addition of copper(I) complexes. In addition, the low reduction potential of unactivated alkyl halides (Ered < -2V vs SCE) hinders the direct single electron transfer (SET) from Cu I catalysts. By contrast, the capture of alkyl radicals by Cu II species and the ensuing reductive elimination of the organocopper(III) complexes can proceed efficiently (Figure ). Figure . The aryl radical activation pathway can enable a new approach for copper-catalyzed cross-coupling of unactivated alkyl halides. Ar•, aryl radical.