Reactivity Patterns of (Protonated) Compound II and Compound I of Cytochrome P450: Which is the better oxidant?
dc.contributor.author
dc.date.accessioned
2017-05-25T07:44:53Z
dc.date.available
2021-04-07T08:03:00Z
dc.date.issued
2017-05-05
dc.identifier.issn
0947-6539
dc.identifier.uri
dc.description.abstract
The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficient. In this work, we present results of a computational study on the reactivity patterns of Compound I, Compound II and protonated Compound II with model substrates and addresses the question, which of those is the most effective oxidant. All calculations, regardless of the substrate, implicate that Compound I is the superior oxidant of the three. However, Compound II and protonated Compound II are found to react with free energies of activation that are only a few kcal mol-1 higher in energy than those obtained with Compound I. Therefore, Compound II and protonated Compound II should be able to react with aliphatic groups with moderate C-H bond strengths. We have analyzed all results in detail and give electronic, thermochemical, valence bond and molecular orbital rationalizations on the reactivity differences and explain experimental product distributions. Overall, the work implies that alternative oxidants could operate alongside Compound I in complex reaction mechanisms of enzymatic and synthetic iron porphyrin complexes
dc.description.sponsorship
VP and MS thanks the support of the Ministerio de Economía y Competitividad of Spain (Projects CTQ2014-54306-P and grant No. BES-2012-052801 to VP),
Generalitat de Catalunya (project number 2014SGR931, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia prizes for MS), and European Fund for Regional Development (FEDER grant UNGI10-4E-801)
dc.format.extent
13 p.
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
info:eu-repo/grantAgreement/MINECO//CTQ2014-54306-P/ES/ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION. NUEVOS DESARROLLOS EN AROMATICIDAD, FUNCIONALES DE LA DENSIDAD Y QUIMICA SUPRAMOLECULAR/
dc.relation.isformatof
Versió postprint del document publicat a: https://doi.org/10.1002/chem.201700363
dc.relation.ispartof
© Chemistry-A European Journal, 2017, vol. 23, núm. 26, p. 6406-6418
dc.relation.ispartofseries
Articles publicats (D-Q)
dc.rights
Tots els drets reservats
dc.source
Li, Xiao-Xi Postils, Verònica Sun, Wei Faponle, Abayomi S. Solà i Puig, Miquel Wang, Yong Nom, Wonwoo de Visser, Sam P. 2017 Reactivity Patterns of (Protonated) Compound II and Compound I of Cytochrome P450: Which is the better oxidant? Chemistry-A European Journal 23 26 6406 6418
dc.subject
dc.title
Reactivity Patterns of (Protonated) Compound II and Compound I of Cytochrome P450: Which is the better oxidant?
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.embargo.terms
2018-05-05
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2018-05-05
dc.type.version
info:eu-repo/semantics/acceptedVersion
dc.identifier.doi
dc.identifier.idgrec
026749
dc.contributor.funder
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3765