A General Strategy for the Nickel-Catalyzed C−H Alkylation of Anilines

The C−H alkylation of aniline derivatives with both primary and secondary alkyl halides was achieved with a versatile nickel catalyst of a vicinal diamine ligand. Step‐economic access to functionalized 2‐pyrimidyl anilines, key structural motifs in anticancer drugs, is thus provided. The C−H functionalization proceeded through facile C−H activation and SET‐type C−X bond cleavage with the assistance of a monodentate directing group, which could be removed in a traceless fashion. One for all: An inexpensive nickel catalyst enables the C−H alkylation of pyrimidyl anilines with both primary and secondary alkyl halides. The directing group (DG) could be easily removed in a traceless fashion, and the products contain key structural motifs of important anticancer drugs.