Catalytic enantioselective syn hydration of enones in water using a DNA-based catalyst

Abstract

The enantioselective addition of water to olefins in an aqueous environment is a common transformation in biological systems, but was beyond the ability of synthetic chemists. Here, we present the first examples of a non-enzymatic catalytic enantioselective hydration of enones, for which we used a catalyst that comprises a copper complex, based on an achiral ligand, non-covalently bound to (deoxy)ribonucleic acid, which is the only source of chirality present under the reaction conditions. The chiral β-hydroxy ketone product was obtained in up to 82% enantiomeric excess. Deuterium-labelling studies demonstrated that the reaction is diastereospecific, with only the syn hydration product formed. So far, this diastereospecific and enantioselective reaction had no equivalent in conventional homogeneous catalysis.

Coronene and pyrene (5, 7)-member ring defects

“…It has been shown previously (Langhoff 1996;Bauschlicher & Langhoff 1997;Boersma et al 2010a) that this combination of a functional basis set and a single-scale factor of 0.958 leads to harmonic frequencies that agree excellently well with experiments. IR spectra, calculated using this level of theory, of molecules for which no experimental data exists are at least consistent with the data of other PAH molecules of the same size and charge (Ricca et al 2011).…”

Bioinspired Catalyst Design and Artificial Metalloenzymes

“…A selection of DNA-binding ligands used by the group of Roelfes with DNA in copper-catalysed asymmetric reactions. [42][43][44][45][46]49] copper complexes and commercially available salmon testes and calf thymus DNA served as catalysts for asymmetric Diels-Alder, [42] Michael addition, [43] and Friedel-Crafts alkylation [44] reactions. By using azachalcone or a,b-unsaturated 2-acyl imidazoles as substrate, high ee values (> 80 %) were reported for these reactions.…”

Asymmetric Catalysis with Helical Polymers

“…[51] In contrast to the other examples of DNA-based catalysis, the first generation ligands, that is, those based on a 9-aminoacridine intercalating moiety, proved to be the most effective ligands for this reaction, giving up to 79 % ee, which could be further improved to 82 % ee by performing the reaction in D 2 O.…”