Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity. Issue 13 (8th March 2016)

• Record Type: Journal Article
• Authors: Contente, Martina L.; Serra, Immacolata; Palazzolo, Luca; Parravicini, Chiara; Gianazza, Elisabetta; Eberini, Ivano; Pinto, Andrea; Guidi, Benedetta; Molinari, Francesco; Romano, Diego
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 13(2016)
• Page Start: 3404
• Page End: 3408
• Publication Date: 2016-03-08
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob00047a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Enantioselective reduction of mono-substituted acetophenones by ketoreductase KRED1-Pglu. 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O length and charge, shape of LUMO frontier molecular orbitals), which can be theoretically calculated.