Cr-Catalyzed Direct ortho-Aminomethylation of Phenols.

We developed a Cr-catalyzed strategy for the regioselective formation of Csp2-Csp3 bonds through the direct and efficient ortho-aminomethylation of N,N-dimethylanilines with phenols. The approach showed excellent site selectivity at the ortho-position of phenols and accommodated broad substrate scope and functional group compatibility for both N,N-dimethylanilines and phenols. Mechanistic studies revealed that the direct ortho-aminomethylation between N,N-dimethylanilines and phenols occurred via an ionic mechanism.