Browsing by Subject "density functional theory"

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    Computational Study of Enantioselective Carboligation Catalyzed by Benzoylformate Decarboxylase
    (ACS, 2019-05) Planas, Ferran; McLeish, Michael J.; Himo, Fahmi; Chemistry and Chemical Biology, School of Science
    Benzoylformate decarboxylase (BFDC) is a thiamin-diphosphate enzyme that catalyzes the decarboxylation of benzoylformate to yield benzaldehyde and carbon dioxide. In addition to its natural reaction, BFDC is able to catalyze carboligation reactions in a highly enantioselective fashion, making the enzyme a potentially important biocatalyst. Here we use density functional theory calculations to investigate the detailed mechanism of BFDC-catalyzed carboligation and to elucidate the sources of the enantioselectivity. Benzaldehyde and acetaldehyde are studied as acceptors, for, when reacting with a benzaldehyde donor, they yield products with opposite enantiospecificity. For each of the acceptors, several possible binding modes to the active site are initially examined before the individual reaction paths leading to the two enantiomeric products are followed. The calculated energies are in good agreement with the experimental results, and the analysis of the transition states gives insight into the origins of the enantioselectivity.