Quinol-Enedione Rearrangement

Abstract

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.