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.

Contente, M., Serra, I., Palazzolo, L., Parravicini, C., Gianazza, E., Eberini, I., et al. (2016). Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity. ORGANIC & BIOMOLECULAR CHEMISTRY, 14(13), 3404-3408 [10.1039/c6ob00047a].

Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity

Serra I.;
2016

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.
Articolo in rivista - Articolo scientifico
acetophenone;Pichia glucozyma; Enzymatic reduction;
English
2016
14
13
3404
3408
none
Contente, M., Serra, I., Palazzolo, L., Parravicini, C., Gianazza, E., Eberini, I., et al. (2016). Enzymatic reduction of acetophenone derivatives with a benzil reductase from Pichia glucozyma (KRED1-Pglu): electronic and steric effects on activity and enantioselectivity. ORGANIC & BIOMOLECULAR CHEMISTRY, 14(13), 3404-3408 [10.1039/c6ob00047a].
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/10281/316390
Citazioni
  • Scopus 23
  • ???jsp.display-item.citation.isi??? 21
Social impact