We present a highly selective protocol for the ortho benzylation of N-aryl amides. This method offers mild conditions, excellent site specificity, and scalability, enabling the synthesis of diarylmethane amides and dibenzoazepines. The protocol allows for one-pot diagonal dibenzylation of dianilides, creating valuable precursors for pharmaceutically active compounds and addressing limitations in current direct C–H activation methodologies.

We report the discovery of a boron-driven ortho-arylation reaction of N-aryl amides and ureas. This novel method enables directed borylation of a wide range of substrates, leading to the synthesis of...