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dc.contributor.authorAbdel-Azeim, Safwat
dc.contributor.authorJedidi, Abdesslem
dc.contributor.authorCavallo, Luigi
dc.contributor.authorEppinger, Jörg
dc.date.accessioned2015-06-28T13:40:03Z
dc.date.available2015-06-28T13:40:03Z
dc.date.issued2015
dc.identifier.citationMechanistic Insights on the Reductive Dehydroxylation Pathway for the Biosynthesis of Isoprenoids Promoted by the IspH Enzyme 2015 Chem. Sci.
dc.identifier.issn2041-6520
dc.identifier.issn2041-6539
dc.identifier.doi10.1039/C5SC01693B
dc.identifier.urihttp://hdl.handle.net/10754/558567
dc.description.abstractHere, we report an integrated quantum mechanics/molecular mechanics (QM/MM) study of the bio-organometallic reaction pathway of the 2H+/2e- reduction of (E)-4-hydroxy-3-methylbut-2-enyl pyrophosphate (HMBPP) into the so called universal terpenoids precursors isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP), promoted by the IspH enzyme. Our results support the viability of the bio-organometallic pathway from rotation of the OH group of HMBPP away from the [Fe4S4] cluster at the core of the catalytic site, to be engaged in a H-bond with Glu126. This rotation is synchronous with π-coordination of the C2=C3 double bond of HMBPP to the apical Fe atom of the [Fe4S4] cluster. Dehydroxylation of HMBPP is triggered by a proton transfer from Glu126 to the OH group of HMBPP. The reaction pathway is completed by competitive proton transfer from the terminal phosphate group to the C2 or C4 atom of HMBPP.
dc.publisherRoyal Society of Chemistry (RSC)
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2015/SC/C5SC01693B
dc.rightsArchived with thanks to Chem. Sci. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. http://creativecommons.org/licenses/by/3.0/
dc.titleMechanistic Insights on the Reductive Dehydroxylation Pathway for the Biosynthesis of Isoprenoids Promoted by the IspH Enzyme
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalChem. Sci.
dc.eprint.versionPost-print
kaust.personAbdel-Azeim, Safwat
kaust.personJedidi, Abdesslem
kaust.personEppinger, Jorg
kaust.personCavallo, Luigi
refterms.dateFOA2018-06-14T08:01:51Z


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