Copper-Mediated Chelation-Assisted Ortho Nitration of (Hetero)arenes

A novel copper-mediated chelation-assisted ortho C–H nitration of (hetero)arenes has been developed for the first time, which used dioxygen as terminal oxidant and 1,2,3-TCP as solvent, leading to the synthesis of nitroaromatics with excellent regioselectivity and in good yields. Mechanistic investigations indicate a mechanism involving a four-centered transition state, with simultaneous cleavage of an ortho C–H bond and a N–O bond of the nitrate anion on the 2-arylpyridine-coordinated copper(II) complex.