One-Step Chemo-, Regio- and Stereoselective Reduction of Ketosteroids to Hydroxysteroids over Zr-Containing MOF-808 Metal-Organic Frameworks.

Zr-containing MOF-808 is a very promising heterogeneous catalyst for the selective reduction of ketosteroids to the corresponding hydroxysteroids through a Meerwein-Ponndorf-Verley (MPV) reaction. Interestingly, the process leads to the diastereoselective synthesis of elusive 17α-hydroxy derivatives in one step, whereas most chemical and biological transformations produce the 17ß-OH compounds, or they require several additional steps to convert 17ß-OH into 17α-OH by inverting the configuration of the 17 center. Moreover, MOF-808 is found to be stable and reusable; it is also chemoselective (only keto groups are reduced, even in the presence of other reducible groups such as C=C bonds) and regioselective (in 3,17-diketosteroids only the keto group in position 17 is reduced, while the 3-keto group remains almost intact). The kinetic rate constant and thermodynamic parameters of estrone reduction to estradiol have been obtained by a detailed temperature-dependent kinetic analysis. The results evidence a major contribution of the entropic term, thus suggesting that the diastereoselectivity of the process is controlled by the confinement of the reaction inside the MOF cavities, where the Zr4+ active sites are located.

Metal-organic and covalent organic frameworks as single-site catalysts.

Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions.

Tuning the Catalytic Properties of UiO-66 Metal-Organic Frameworks: From Lewis to Defect-Induced Brønsted Acidity.

The Lewis/Brønsted acidity and catalytic properties of UiO-66-type metal-organic frameworks are studied in the context of tunable acid catalysts based on the presence of linker defects that create coordinatively unsaturated Zr4+ centers. Fourier transform infrared spectroscopy of adsorbed CO and direct pH measurements are employed to characterize hydrated and dehydrated UiO-66 containing different number of Zr4+ sites associated with defects. These sites can strongly polarize coordinated water molecules, which induces Brønsted acidity in the hydrated material. Upon dehydration of the solid, the coordinated water molecules are removed, and the underlying coordinatively unsaturated Zr4+ cations become exposed and available as Lewis acid sites. Herein we show, for various acid-catalyzed reactions, how it is possible to shift from a Brønsted acid to a Lewis acid catalyst by simply controlling the hydration degree of the solid. This control adds a new dimension to the design and engineering of MOFs for catalytic applications.

Free radical activity of natural and heat treated amphibole asbestos.

The amphibole minerals amosite and crocidolite were subjected to calcination and to hydrothermal treatment in order to study the effect of these heat treatments on the ability of the minerals to trigger formation of free radicals, which is known to be a main factor causing asbestosis and other asbestos-induced diseases. Free radical activity of the natural and heat treated minerals was studied by using supercoiled DNA (pUC18 plasmid) as a target molecule, and also by means of EPR spectroscopy. It was shown that after calcination of the natural minerals at 1073 K their free radical activity was strongly decreased These results, which may have relevant consequences for asbestos technology, were correlated with concomitant alteration of the structure and surface chemistry of the minerals during calcination.

MOFs as multifunctional catalysts: one-pot synthesis of menthol from citronellal over a bifunctional MIL-101 catalyst.

A bifunctional MOF catalyst containing coordinatively unsaturated Cr(3+) sites and palladium nanoparticles (Pd@MIL-101) has been used for the cyclization of citronellal to isopulegol and for the one-pot tandem isomerization/hydrogenation of citronellal to menthol. The MOF was found to be stable under the reaction conditions used, and the results obtained indicate that the performance of this bifunctional solid catalyst is comparable with other state-of-the-art materials for the tandem reaction: Full citronellal conversion was attained over Pd@MIL-101 in 18 h, with 86% selectivity to menthols and a diastereoselectivity of 81% to the desired (-)-menthol, while up to 30 h were necessary for attaining similar values over Ir/H-beta under analogous reaction conditions.