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Quantum chemical modeling studies of ethylbenzene dehydrogenase activity
Author(s) -
Szaleniec Maciej,
Salwiński Aleksander,
Borowski Tomasz,
Heider Johann,
Witko Malgorzata
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23143
Subject(s) - ethylbenzene , chemistry , reactivity (psychology) , quantum chemical , dehydrogenation , quantum chemistry , electrophile , stereoselectivity , styrene , computational chemistry , biocatalysis , reaction mechanism , carbocation , photochemistry , organic chemistry , catalysis , molecule , medicine , polymer , alternative medicine , pathology , copolymer
Quantum chemical modeling is used to predict the reactivity of ethylbenzene dehydrogenase (EBDH), a molybdenum enzyme that catalyzes the stereoselective oxidation of alkylaromatic and alkylheterocyclic hydrocarbons to the ( S )‐enantiomers of secondary alcohols. The reaction mechanism is studied for four different substrates: ethylbenzene, 4‐ethylphenol, allylbenzene, and 4‐ethylpyridine with a cluster model of the active site. The modeling predicts radical CH activation followed by the formation of a radical intermediate product. Then another electron is transferred to form a carbocation species in TS2, followed by a tightly associated OH rebound step. The modeling study allows qualitative correlation of energy barriers with the results of kinetic assays and identifies factors influencing the chemical reactivity of EBDH with different substrates. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011.