title: Enantioselective Catalysis by Using Short, Structurally Defined DNA Hairpins as Scaffold for Hybrid Catalysts.
abstract: A new type of DNA metal complex hybrid catalyst, which is based on single-stranded DNA oligonucleotides, is described. It was shown that oligonucleotides as short as 14 nucleotides that fold into hairpin structures are suitable as nucleic acid components for DNA hybrid catalysts. With these catalysts, excellent enantioinduction in asymmetric Diels-Alder reactions with selectivity values as high as 96 % enantiomeric excess (ee) can be achieved. Molecular dynamics simulations indicate that a rather flexible loop combined with a rigid stem region provides DNA scaffolds with these high selectivity values.
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, 48149, Münster, Germany.
authors.forename: Jasmin J
authors.initials: JJ
authors.lastname: Marek
authors.affiliation: Institut für Physikalische Chemie, Westfälische Wilhelms-Universität, Corrensstrasse 28/30, 48149, Münster, Germany.
authors.forename: Raghvendra P
authors.initials: RP
authors.lastname: Singh
authors.affiliation: Institut für Physikalische Chemie, Westfälische Wilhelms-Universität, Corrensstrasse 28/30, 48149, Münster, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Heuer
authors.affiliation: Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Corrensstrasse 40, 48149, Münster, Germany.
authors.forename: Ulrich
authors.identifier: http://orcid.org/0000-0002-4904-6793
authors.initials: U
authors.lastname: Hennecke
mesh_terms: D001483:Base Sequence; D002384:Catalysis; D002942:Circular Dichroism; D056831:Coordination Complexes / Q000737:chemistry* / Q000378:metabolism; D061565:Cycloaddition Reaction; D004277:DNA, Single-Stranded / Q000737:chemistry* / Q000378:metabolism; D009690:Nucleic Acid Conformation; D009841:Oligonucleotides / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D056831:Coordination Complexes; D004277:DNA, Single-Stranded; D009841:Oligonucleotides
keywords: DNA; asymmetric catalysis; bioorganic chemistry; cycloaddition; molecular modeling