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.
Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity / M.L. Contente, I. Serra, L. Palazzolo, C. Parravicini, E. Gianazza, I. Eberini, A. Pinto, B. Guidi, F. Molinari, D. Romano. - In: ORGANIC & BIOMOLECULAR CHEMISTRY. - ISSN 1477-0539. - 14:13(2016), pp. 3404-3408.
|Titolo:||Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity|
CONTENTE, MARTINA LETIZIA (Primo)
SERRA, IMMACOLATA (Secondo)
MOLINARI, FRANCESCO ENZO (Penultimo)
ROMANO, DIEGO (Ultimo)
|Parole Chiave:||tenuis xylose reductase; alcohol-dehydrogenase; aromatic ketones; ADH|
|Settore Scientifico Disciplinare:||Settore CHIM/11 - Chimica e Biotecnologia delle Fermentazioni|
Settore CHIM/08 - Chimica Farmaceutica
Settore BIO/10 - Biochimica
|Data di pubblicazione:||2016|
|Digital Object Identifier (DOI):||http://dx.doi.org/10.1039/c6ob00047a|
|Appare nelle tipologie:||01 - Articolo su periodico|