Origin of the Enhanced Reactivity in the ortho C–H Borylation of Benzaldehydes with BBr3

The metal-free ortho C–H borylation of benzaldehyde derivatives using a transient imine directing group was recently developed by our group, providing an efficient strategy for the synthesis of organoboron reagents. Herein, we report on an extensive investigation of the reaction mechanism using density functional theory (DFT) calculations. Computations for the reaction pathway with various imine substrates, as well as the effect of an added base were examined, and the experimentally observed reactivity enhancement is proposed to originate from the tunability of the destabilizing strain energies that results in a reversible complexation process with BBr3.