Theoretical Studies on Pd(II)-Catalyzed meta-Selective C–H Bond Arylation of Arenes

Direct C–H arylation of arene is often the most efficient way to construct a biaryl product. However, meta-selective C–H arylation is much less reported than ortho selectivity. In this work, DFT studies have been performed to systematically investigate the factors that may affect the competition between meta and ortho selectivity. Our results suggest that a weak directing group is essential to suppress the commonly observed CMD on ortho position, so that the meta position can be activated by a migratory insertion pathway. In addition, we find that naphthyl substrates are more likely to undergo a migratory insertion due to its significantly lower dearomatization energy, and a more oxidizing metal can promote the migratory insertion pathway by lowering the succeeding reductive deprotonation.