Nickel-catalyzed site-selective alkylation of unactivated C(sp ³)-H bonds

The direct alkylation of unactivated sp³ C-H bonds of aliphatic amides was achieved via nickel catalysis with the assist of a bidentate directing group. The reaction favors the C-H bonds of methyl groups over the methylene C-H bonds and tolerates various functional groups. Moreover, this reaction shows a predominant preference for sp³ C-H bonds of methyl groups via a five-membered ring intermediate over the sp² C-H bonds of arenes in the cyclometalation step.