title: DNA-Accelerated Catalysis of Carbene-Transfer Reactions by a DNA/Cationic Iron Porphyrin Hybrid.
abstract: A novel DNA-based hybrid catalyst comprised of salmon testes DNA and an iron(III) complex of a cationic meso-tetrakis(N-alkylpyridyl)porphyrin was developed. When the N-methyl substituents were placed at the ortho position with respect to the porphyrin ring, high reactivity in catalytic carbene-transfer reactions was observed under mild conditions, as demonstrated in the catalytic enantioselective cyclopropanation of styrene derivatives with ethyl diazoacetate (EDA) as the carbene precursor. A remarkable feature of this catalytic system is the large DNA-induced rate acceleration observed in this reaction and the related dimerization of EDA. It is proposed that high effective molarity of all components of the reaction in or near the DNA is one of the key contributors to this unique reactivity. This study demonstrates that the concept of DNA-based asymmetric catalysis can be expanded into the realm of organometallic chemistry.
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Ana
authors.initials: A
authors.lastname: Rioz-Martínez
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Jens
authors.initials: J
authors.lastname: Oelerich
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands.
authors.forename: Nathalie
authors.initials: N
authors.lastname: Ségaud
authors.affiliation: Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG, Groningen, The Netherlands. j.g.roelfes@rug.nl.
authors.forename: Gerard
authors.identifier: 0000-0002-0364-9564
authors.initials: G
authors.lastname: Roelfes
mesh_terms: D000818:Animals; D002384:Catalysis; D002412:Cations / Q000737:chemistry; D004247:DNA / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D008297:Male; D008665:Metalloporphyrins / Q000737:chemistry*; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D015394:Molecular Structure; D012474:Salmon; D013737:Testis / Q000737:chemistry*
chemical_list: D002412:Cations; D008665:Metalloporphyrins; C030011:carbene; D004247:DNA; D007501:Iron; D008697:Methane
keywords: DNA; carbenes; cyclopropanation; hybrid catalysts; porphyrins