Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids

Abstract

We report herein a method for the oxidative dearomatization of phenols and bare polycyclic arenes into the corresponding quinoid derivatives using hydrogen peroxide. The reaction is catalyzed by sulfonic acids and best results were achieved using heterogenized species. The best results using phenols were achieved using a hybrid material, namely a perfluorinated polymer functionalized with sulfonic acid groups supported on silica. The dearomatization of polycyclic aromatic hydrocarbons performed better using the polymeric acid catalyst. These methods operate under mild conditions, using mild and benign oxidants and thus minimizing the formation of waste.

Allylations of aryl/heteroaryl ketones: neat, clean, and sustainable. Applications to targets in the pharma- and nutraceutical industries

“…These couplings were predicated on the original route championed by Ruttiman, 21 who devised a clever Diels–Alder/retro-Diels–Alder scheme. Using 2-methylnaphthoquinone, readily obtained via oxidation of 2-methylnaphthalene, 22 Diels–Alder (DA) addition of cyclopentadiene (Cp) leads to adduct 32 which is perfectly situated for subsequent monoallylation (Scheme 5). In the originally described procedure, 21 diketone adduct 32 was treated with base and phytyl bromide to give vitamin K 1 .…”

Organocatalytic activation of hydrogen peroxide: towards green and sustainable oxidations

“…The presence of a polar, water-soluble solvent was imperative for the effective dearomatisation of phenols 206 to quinones 207 ( Scheme 49A ). 119 In order to incorporate naphthalenes 208 and some polycyclic arenes in this method, re-optimisation of the reaction conditions led to an unsupported polymeric sulfonic acid as the catalyst and an increase of the oxidant and temperature ( Scheme 49A ). Vitamin K 3 210 was successfully retrieved almost quantitively from 2-methylnaphthalene ( Scheme 49B ).…”

Copper and Cobalt Co‐catalyzed Selective Electrooxidation of Phenol to p‐Benzoquinone Under Mild Conditions

“…[14] The oxidative dearomatization of phenol into p-benzoquinone was achieved using hydrogen peroxide triggered by heterogeneous sulfonic acid catalyst and 74 % pbenzoquinone was obtained. [15] It has been reported that phenol could be oxidized into benzoquinone on the platinum electrode with the modulated alternating voltage and the yield of p-benzoquinone was about 43 %. [16] Recently, Han et al reported that the production of p-benzoquinone from phenol using nitrogen-doped hierarchically porous carbon-supported FeRu catalyst with simultaneous production of cyclohexanone, and the conversion of phenol was 43 % with 99 % selectivity of p-benzoquinone.…”

“…Polymer‐anchored complexes were also reported to catalyze oxidation of phenol and hydroquinone for p ‐benzoquinone using 30 % H 2 O 2 as the oxidant with 14.4 % yield [14] . The oxidative dearomatization of phenol into p ‐benzoquinone was achieved using hydrogen peroxide triggered by heterogeneous sulfonic acid catalyst and 74 % p ‐benzoquinone was obtained [15] . It has been reported that phenol could be oxidized into benzoquinone on the platinum electrode with the modulated alternating voltage and the yield of p ‐benzoquinone was about 43 % [16] .…”