| Abstract: | We have developed a highly efficient aryl migration from an aryl ether to a carboxylic acid group through retro‐Smiles rearrangement by visible‐light photoredox catalysis at ambient temperature. Transition metals and a stoichiometric oxidant and base are avoided in the transformation. Inspired by the high efficiency of this transformation and the fundamental importance of C?O bond cleavage, we developed a novel approach to the C?O cleavage of a biaryl ether to form two phenolic compounds, as demonstrated by a one‐pot, two‐step gram‐scale reaction under mild conditions. The aryl migration exhibits broad scope and can be applied to the synthesis of pharmaceutical compounds, such as guacetisal. Primary mechanistic studies indicate that the catalytic cycle occurs by a reductive quenching pathway. |
