Chemoselective, iron(ii)-catalyzed oxidation of a variety of secondary alcohols over primary alcohols utilizing H2O2 as the oxidant

Abstract

A mild, iron-based catalyst system is presented that selectively oxidizes secondary alcohols to the corresponding hydroxy ketones in the presence of primary alcohols within 15 minutes at room temperature, utilizing H2O2 as the oxidant.

Solvent-Free Microwave-Assisted Peroxidative Oxidation of Alcohols Catalyzed by Iron(III)-TEMPO Catalytic Systems

“…Very recently, some of us reported very efficient catalytic systems based on copper(II) [7][8][9][10] and Fe(III) [11][12][13][14] complexes for the peroxidative (using TBHP) oxidation of different primary and secondary alcohols, including a solvent-free MW assisted method which accelerates dramatically the reaction rate using a very low MW irradiation power. The selective oxidation, with a Fe complex, of a secondary alcohol when a primary one is present in the same molecule was also reported [14]. However, the catalyst recycling and reuse was not achieved in those systems.…”

“…Many catalytic methods have been developed for the oxidation of alcohols, the most commonly utilizing homogeneous catalysts based on different transition metals, such as Co [3], Mn [4,5], V [6], Cu [7][8][9][10], Fe [11][12][13][14], Mo [14], Ru [16,17], and Pd [18]. Unfortunately, most of the Electronic supplementary material The online version of this article (doi:10.1007/s10562-015-1616-2) contains supplementary material, which is available to authorized users.…”

“…Moreover, they suffer from the usual separation and recycling difficulties inherent to homogenous catalytic system. To eliminate the harmful wastes, the development of catalytic oxidation procedures that involve green oxidants, in particular dioxygen or peroxides [H 2 O 2 , tert-butylhydroperoxide ( t BuOOH or TBHP)], is a matter of current interest [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Immobilization of Ru(terpyridine)(2,6‐pyridinedicarboxylate) onto MCM‐41 and its catalysis in the oxidation of alcohols

“…The immobilized ruthenium complex was also applied to the oxidation of primary benzylic alcohols with TBHP as oxidant to see whether it was possible to obtain selectivity towards either the aldehyde or the carboxylic acid. Unfortunately, the selectivity is not controlled; only carboxylic acids as main products are obtained in all the cases ( Table 6, entries [17][18][19]. However, primary heterocyclic alcohols including 2-pyridylmethanol and 5-hydroxymethylfurfural are converted to their corresponding aldehydes in moderate yield at 40°C (Table 6, entries 20 and 21); no deep oxidation products are observed in these cases.…”

“…These oxidants in combination with transition metals or their complexes have been found to be very efficient in the oxidation of secondary alcohols to the corresponding ketones. [13][14][15][16][17][18][19] In 2007, Beller and co-workers [20] applied Ru(terpyridine)(2,6pyridinedicarboxylate) -Ru(terpy)(pydic)to the oxidation of secondary alcohols to their corresponding ketones using hydrogen peroxide as oxidant. This complex showed excellent performance in the reaction in the absence of co-catalysts or organic solvents.…”