Mixed-ligand aminoalcohol-dicarboxylate copper(II) coordination polymers as catalysts for the oxidative functionalization of cyclic alkanes and alkenes

Abstract

AbstractNew copper(II) catalytic systems for the mild oxidative C–H functionalization of cycloalkanes and cycloalkenes were developed, which are based on a series of mixed-ligand aminoalcohol-dicarboxylate coordination polymers, namely [Cu2(μ-dmea)2(μ-nda)(H2O)2]n·2nH2O (1), [Cu2(μ-Hmdea)2(μ-nda)]n·2nH2O (2), and [Cu2(μ-Hbdea)2(μ-nda)]n·2nH2O (3) that bear slightly different dicopper(II) aminoalcoholate cores, as well as on a structurally distinct dicopper(II) [Cu2(H4etda)2(μ-nda)]·nda·4H2O (4) derivative [abbreviations: H2nda, 2,6-naphthalenedicarboxylic acid; Hdmea,N,N′-dimethylethanolamine; H2mdea,N-methyldiethanolamine; H2bdea,N-butyldiethanolamine; H4etda,N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine]. Compounds1–4act as homogeneous catalysts in the three types of model catalytic reactions that proceed in aqueous acetonitrile medium under mild conditions (50–60°C): (i) the oxidation of cyclohexane by hydrogen peroxide to cyclohexyl hydroperoxide, cyclohexanol, and cyclohexanone, (ii) the oxidation of cycloalkenes (cyclohexene, cyclooctene) by hydrogen peroxide to a mixture of different oxidation products, and (iii) the single-pot hydrocarboxylation of cycloalkanes (cyclopentane, cyclohexane, cycloheptane, cyclooctane) by carbon monoxide, water, and a peroxodisulfate oxidant into the corresponding cycloalkanecarboxylic acids. The catalyst and substrate scope as well as some mechanistic features were investigated; the highest catalytic activity of1–4was observed in the hydrocarboxylation of cycloalkanes, allowing to achieve up to 50% total product yields (based on substrate).