title: Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity.
abstract: A recombinant ketoreductase from Pichia glucozyma (KRED1-Pglu) was used for the enantioselective reduction of various mono-substituted acetophenones. Reaction rates of meta- and para-derivatives were consistent with the electronic effects described by σ-Hammett coefficients; on the other hand, enantioselectivity was determined by an opposite orientation of the substrate in the binding pocket. Reduction of ortho-derivatives occurred only with substrates bearing substituents with low steric impact (i.e., F and CN). Reactivity was controlled by stereoelectronic features (C[double bond, length as m-dash]O length and charge, shape of LUMO frontier molecular orbitals), which can be theoretically calculated.
authors.affiliation: Department of Food, Nutritional and Environmental Sciences (DeFENS), University of Milan, Via Mangiagalli 25, 20133 Milano, Italy. diego.romano@unimi.it.
authors.forename: Martina L
authors.initials: ML
authors.lastname: Contente
authors.forename: Immacolata
authors.initials: I
authors.lastname: Serra
authors.forename: Luca
authors.initials: L
authors.lastname: Palazzolo
authors.forename: Chiara
authors.initials: C
authors.lastname: Parravicini
authors.forename: Elisabetta
authors.initials: E
authors.lastname: Gianazza
authors.forename: Ivano
authors.initials: I
authors.lastname: Eberini
authors.forename: Andrea
authors.initials: A
authors.lastname: Pinto
authors.forename: Benedetta
authors.initials: B
authors.lastname: Guidi
authors.forename: Francesco
authors.initials: F
authors.lastname: Molinari
authors.forename: Diego
authors.initials: D
authors.lastname: Romano
mesh_terms: D000098:Acetophenones / Q000737:chemistry / Q000378:metabolism*; D000429:Alcohol Oxidoreductases / Q000737:chemistry / Q000378:metabolism*; D004583:Electrons; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010843:Pichia / Q000201:enzymology*; D013237:Stereoisomerism; D013379:Substrate Specificity
chemical_list: D000098:Acetophenones; D000429:Alcohol Oxidoreductases; C446000:benzil reductase