High Ortho Preference in Ni-Catalyzed Cross-Coupling of Halophenols with Alkyl Grignard Reagents

High preference of substitution at the position ortho to the hydroxy group was observed for Ni-catalyzed cross-coupling reactions of dihalophenols with alkyl Grignard reagents. Reactions of 2,4-dihalophenols, with various combinations of F, Cl, and Br, were shown to afford ortho-cross-coupled products selectively. In addition, high ortho preference was also observed in competitive cross-coupling reactions between 2-halophenols and other halophenols.