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

• Published in: Nature chemistry Vol. 2; no. 11; pp. 991 - 995
• Main Authors: Boersma, Arnold J., Coquière, David, Geerdink, Danny, Rosati, Fiora, Feringa, Ben L., Roelfes, Gerard
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 01.11.2010; Nature Publishing Group
• Subjects: 639/638/403/935; 639/638/549; 639/638/77; Alkenes - chemistry; Analytical Chemistry; Biochemistry; Catalysis; Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Chromatography, High Pressure Liquid; Copper; Deuterium; DNA - chemistry; Hydration; Inorganic Chemistry; Ketones; Ligands; Organic Chemistry; Physical Chemistry; Stereoisomerism; Water - chemistry
• ISSN: 1755-4330; 1755-4349
• DOI: 10.1038/nchem.819

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. Nature frequently shows exquisite control over reactions both of water and in water. Here, the enantioselective conjugate addition of water to an enone — a reaction that has no equivalent in conventional homogeneous catalysis — is catalysed by a copper complex of an achiral ligand that is non-covalently bound to DNA.