Regioselective Alkylative Cross-Coupling of Remote Unactivated C( sp 3 )–H Bonds

The functionalization of unactivated C( sp 3 )–H bonds poses a significant challenge due to their ubiquity and relative similarity in most organic frameworks. Herein, we describe the use of a combined photoredox and nickel catalytic system for the regioselective C( sp 3 )–C( sp 3 ) coupling of unactivated C( sp 3 )–H bonds and alkyl bromides. Positional selectivity is dictated by a 1,5-hydrogen atom transfer (HAT) reaction by a pendent amide. Interception of this radical by a Ni catalyst allows distal alkylation to occur in good yield and excellent selectivity.