Quinol–Enedione Rearrangement

The quinol–enedione rearrangement enables the
synthesis
of 2-cyclohexene-1,4-diones from readily available para-quinol substrates. Building on sporadic early reports of this transformation,
we have optimized the reaction conditions and systematically investigated
its substrate scope. The utility of Brønsted acid-mediated reaction
conditions for a variety of quinol derivatives, including those with
substituted and unsubstituted migrating termini, is highlighted. Notably,
kinetic selectivity between quinol–enedione and dienone–phenol
rearrangements is demonstrated. The synthetic potential of the enedione
products is showcased through a range of transformations, leading
to the formation of complex polycyclic structures. These findings
provide a valuable framework for recognizing and applying the quinol–enedione
rearrangement in synthesis, while computational studies offer valuable
insights into its mechanistic underpinnings.