title: Halogenase-Inspired Oxidative Chlorination Using Flavin Photocatalysis.
abstract: Chlorine gas or electropositive chlorine reagents are used to prepare chlorinated aromatic compounds, which are found in pharmaceuticals, agrochemicals, and polymers, and serve as synthetic precursors for metal-catalyzed cross-couplings. Nature chlorinates with chloride anions, FAD-dependent halogenases, and O2 as the oxidant. A photocatalytic oxidative chlorination is described based on the organic dye riboflavin tetraacetate mimicking the enzymatic process. The chemical process allows within the suitable arene redox potential window a broader substrate scope compared to the specific activation in the enzymatic binding pocket.
authors.affiliation: Universität Regensburg, Fakultät für Chemie und Pharmazie, 93040, Regensburg, Germany.
authors.forename: Thea
authors.initials: T
authors.lastname: Hering
authors.affiliation: Universität Regensburg, Fakultät für Chemie und Pharmazie, 93040, Regensburg, Germany.
authors.forename: Bernd
authors.initials: B
authors.lastname: Mühldorf
authors.affiliation: Universität Regensburg, Fakultät für Chemie und Pharmazie, 93040, Regensburg, Germany. robert.wolf@ur.de.
authors.forename: Robert
authors.identifier: http://orcid.org/0000-0003-4066-6483
authors.initials: R
authors.lastname: Wolf
authors.affiliation: Universität Regensburg, Fakultät für Chemie und Pharmazie, 93040, Regensburg, Germany. burkhard.koenig@ur.de.
authors.forename: Burkhard
authors.identifier: http://orcid.org/0000-0002-6131-4850
authors.initials: B
authors.lastname: König
mesh_terms: D040761:Biomimetic Materials / Q000737:chemistry*; D002384:Catalysis; D002713:Chlorine / Q000737:chemistry*; D004396:Coloring Agents / Q000737:chemistry*; D005182:Flavin-Adenine Dinucleotide / Q000737:chemistry*; D054879:Halogenation; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D006867:Hydrolases / Q000737:chemistry; D008027:Light; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D012256:Riboflavin / Q000031:analogs & derivatives* / Q000737:chemistry
chemical_list: D004396:Coloring Agents; D006841:Hydrocarbons, Aromatic; D005182:Flavin-Adenine Dinucleotide; C058357:2',3',4',5'-tetraacetylriboflavin; D002713:Chlorine; D006867:Hydrolases; C046137:haloalkane dehalogenase; D010100:Oxygen; D012256:Riboflavin
keywords: chlorination photocatalysis; enzyme models; flavins; oxidative