<i>Ortho</i> – <i>Meta</i> and <i>Para</i> – <i>Meta</i> Isomerization of Phenols

Phenols are ubiquitous structural motifs in pharmaceuticals, natural products, and agrochemicals. The substitution pattern of a given phenol has an obvious impact on its physical and biological properties. As such, synthetic approaches to positional isomerization of phenols are highly desirable, offering a way to edit molecular shape at a late stage. We present an approach to the <i>para</i>-<i>meta</i> and <i>ortho</i>-<i>meta</i> isomerization of phenols, combining oxidative dearomatization with photochemical rearrangement and reductive aromatization. This method allows the transposition of neighboring carbon atoms within the aromatic core. We enable access to challenging <i>meta</i>-functionalized phenols from readily available <i>para</i> and <i>ortho</i> isomers. In doing so, we edit the shape of medicinally relevant structures without altering the functionality.