Skip navigation
Skip navigation

Toward a consistent mechanism for diol dehydratase catalyzed reactions: an application of the partial-proton-transfer concept

Trebeck, Katherine; Golding, Bernard; Radom, Leo

Description

Ab initio molecular orbital theory has been used to study the reactions catalyzed by the B12-dependent enzyme diol dehydratase. The calculations show that a pathway involving the 1,2-shift of a hydroxyl group is greatly facilitated by partial proton transfer to the migrating oxygen. These results suggest a conceptually simple mechanism for the rearrangement whose reaction rate is consistent with experiment. The inclusion of a gem-diol intermediate in the proposed pathway is in accordance...[Show more]

dc.contributor.authorTrebeck, Katherine
dc.contributor.authorGolding, Bernard
dc.contributor.authorRadom, Leo
dc.date.accessioned2015-12-13T23:35:16Z
dc.identifier.issn0002-7863
dc.identifier.urihttp://hdl.handle.net/1885/93837
dc.description.abstractAb initio molecular orbital theory has been used to study the reactions catalyzed by the B12-dependent enzyme diol dehydratase. The calculations show that a pathway involving the 1,2-shift of a hydroxyl group is greatly facilitated by partial proton transfer to the migrating oxygen. These results suggest a conceptually simple mechanism for the rearrangement whose reaction rate is consistent with experiment. The inclusion of a gem-diol intermediate in the proposed pathway is in accordance with18O-labeling experiments and thus overcomes important shortcomings in previously proposed mechanisms.
dc.publisherAmerican Chemical Society
dc.sourceJournal of the American Chemical Society
dc.subjectKeywords: acetaldehyde; cobamamide; diol dehydratase; ethylene glycol; hydrolyase; unclassified drug; article; catalysis; enzyme activity; enzyme substrate complex; proton transport
dc.titleToward a consistent mechanism for diol dehydratase catalyzed reactions: an application of the partial-proton-transfer concept
dc.typeJournal article
local.description.notesImported from ARIES
local.description.refereedYes
local.identifier.citationvolume121
dc.date.issued1999
local.identifier.absfor030601 - Catalysis and Mechanisms of Reactions
local.identifier.ariespublicationMigratedxPub25256
local.type.statusPublished Version
local.contributor.affiliationTrebeck, Katherine, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationGolding, Bernard, Newcastle University
local.contributor.affiliationRadom, Leo, College of Physical and Mathematical Sciences, ANU
local.description.embargo2037-12-31
local.bibliographicCitation.startpage5700
local.bibliographicCitation.lastpage5704
local.identifier.doi10.1021/ja990209g
dc.date.updated2015-12-12T09:39:18Z
local.identifier.scopusID2-s2.0-0033597609
CollectionsANU Research Publications

Download

File Description SizeFormat Image
01_Trebeck_Toward_a_consistent_mechanism_1999.pdf133.59 kBAdobe PDF    Request a copy


Items in Open Research are protected by copyright, with all rights reserved, unless otherwise indicated.

Updated:  19 May 2020/ Responsible Officer:  University Librarian/ Page Contact:  Library Systems & Web Coordinator