Thermodynamic-Kinetic Comparison of Palladium(II)-Mediated Alcohol and Hydroquinone Oxidation.

Abstract

Palladium(II) catalysts promote oxidative dehydrogenation and dehydrogenative coupling of many organic molecules. Oxidations of alcohols to aldehydes or ketones are prominent examples. Hydroquinone (H2Q) oxidation to benzoquinone (BQ) is conceptually related to alcohol oxidation, but it is significantly more challenging thermodynamically. The BQ/H2Q redox potential is sufficiently high that BQ is often used as an oxidant in Pd-catalyzed oxidation reactions. A recent report (J. Am Chem. Soc. 2020, 142, 19678-19688) showed that certain ancillary ligands can raise the PdII/0 redox potential sufficiently to reverse this reactivity, enabling (L)PdII(OAc)2 to oxidize hydroquinone to benzoquinone. Here, we investigate the oxidation of tert-butylhydroquinone ( t BuH2Q) and 4-fluorobenzyl alcohol (4FBnOH), mediated by (bc)Pd(OAc)2 (bc = bathocuproine). Although alcohol oxidation is thermodynamically favored over H2Q oxidation by more than 400 mV, the oxidation of t BuH2Q proceeds several orders of magnitude faster than 4FBnOH oxidation. Kinetic and mechanistic studies reveal that these reactions feature different rate-limiting steps. Alcohol oxidation proceeds via rate-limiting β-hydride elimination from a PdII-alkoxide intermediate, while H2Q oxidation features rate-limiting isomerization from an O-to-C-bound PdII-hydroquinonate species. The enhanced rate of H2Q oxidation reflects the kinetic facility of O─H relative to C─H bond cleavage.