Nickel-electrocatalysed C(sp³)–C(sp³) cross-coupling of unactivated alkyl halides

The C(sp³)–C(sp³) linkages are undoubtedly important in natural products, pharmaceuticals and organic compounds. Electrochemical cross-electrophile coupling with a broad range of available alkyl halides is an attractive and useful strategy for the construction of C(sp³)–C(sp³) bonds, although success could only be seen on activated alkyl halides in previous reports, due to the great challenge of reactivity and selectivity control of unactivated alkyl halides. Here we report a general strategy for electrochemical cross-electrophile coupling of unactivated alkyl halides under nickel catalysis. The highly selective electrochemical cross-electrophile coupling process was carried out in an operationally simple manner with high selectivity, setting the stage for the challenging C(sp³)–C(sp³) bonds construction with versatile unactivated alkyl halides, including the cross-coupling of primary–primary halides, primary–secondary halides, primary–tertiary halides and secondary–secondary halides with high selectivity and excellent functional group compatibility. The diverse products, as well as the various late-stage modifications of bio-relevant compounds, demonstrated its potential use in organic synthesis and pharmaceutical chemistry. (Figure presented.)