Oxidation of alkenes with non-heme iron complexes: suitability as an organic synthetic method

In the course of a preliminary study to determine the preparative value and the synthetic applications of the non-heme iron(II) complexes Fe(bpmen)(OTf)(2) and Fe(tpa)(OTf)(2), in particular the oxidation of alkenes by using hydrogen peroxide as the terminal oxidant, we have found significant differences in catalyst behavior. After several attempts it was clear that the preparative relevance of the oxidation processes was linked to the concentration of the catalyst and optimal results were obtained when the concentration value was 5 mol %. At that concentration, the Fe(bpmen)(OTf)(2) catalyst mostly gave rise to mixtures of the epoxide and the trans-dihydroxylation products formed by water-assisted hydrolytic cleavage of the epoxides. Furthermore, the use of the tripodal ligand tpa led to cis dihydroxylation products. When deactivated olefins were used as substrates for the oxidation reaction, the cis-diols were obtained exclusively, although with modest conversions, regardless of the catalyst used. (C) 2014 Elsevier Ltd. All rights reserved.