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Can electrostatic catalysis of Diels-Alder reactions be harnessed with pH-switchable charged functional groups?

Aitken, Heather; Coote, Michelle

Description

Quantum-chemical calculations at the M06-2X/6-31+G(d,p) and G3(MP2)CC levels of theory are used to assess the feasibility of harnessing charged functional groups to electrostatically catalyse Diels–Alder reactions and alter their regio selectivity. For the reaction of the polar diene 2-pyrone with substituted cyclopentene, pH switches of nearly 60 kJ mol−1 are observed in the gas-phase. To switch regioselectivity however it is necessary to toggle between negatively and positively charged...[Show more]

dc.contributor.authorAitken, Heather
dc.contributor.authorCoote, Michelle
dc.date.accessioned2019-05-06T23:48:48Z
dc.identifier.issn1463-9076
dc.identifier.urihttp://hdl.handle.net/1885/160871
dc.description.abstractQuantum-chemical calculations at the M06-2X/6-31+G(d,p) and G3(MP2)CC levels of theory are used to assess the feasibility of harnessing charged functional groups to electrostatically catalyse Diels–Alder reactions and alter their regio selectivity. For the reaction of the polar diene 2-pyrone with substituted cyclopentene, pH switches of nearly 60 kJ mol−1 are observed in the gas-phase. To switch regioselectivity however it is necessary to toggle between negatively and positively charged functional groups. With the 6-membered cyclohexene derivatives, similar pH-switches are observed but this time an opportunity to pH-switch diastereomeric selectivity is also observed due to the asymmetry of the transition state. When 2-pyrone was replaced with a non-polar diene, cyclopentadiene, pH switches were understandably smaller but still substantial (ca. 15 kJ mol−1). Likewise pH switches are attenuated by solvent but remain substantial (ca. 30 kJ mol−1) in toluene and synthetically useful (ca. 15 kJ mol−1) even in moderately low polar solvents such as dichloromethane.
dc.description.sponsorshipM. L. C. gratefully acknowledges an ARC Laureate Fellowship and generous allocations on the National Facility of the Australian National Computational Infrastructure.
dc.format.extent6 pages
dc.format.mimetypeapplication/pdf
dc.language.isoen_AU
dc.publisherRoyal Society of Chemistry
dc.rights© 2018 Royal Society of Chemistry
dc.sourcePhysical Chemistry Chemical Physics
dc.subjectQuantum-chemical calculations
dc.subjectDiels–Alder reactions
dc.subjectelectrostatically catalyse
dc.titleCan electrostatic catalysis of Diels-Alder reactions be harnessed with pH-switchable charged functional groups?
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume20
dcterms.dateAccepted2017-11-30
dc.date.issued2018
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.ariespublicationu4917478xPUB1
local.publisher.urlhttps://www.rsc.org/
local.type.statusAccepted Version
local.contributor.affiliationAitken, Heather, College of Science, The Australian National University
local.contributor.affiliationCoote, Michelle, College of Science, The Australian National University
dc.relationhttp://purl.org/au-research/grants/arc/FL170100041
local.identifier.essn1463-9084
local.bibliographicCitation.issue16
local.bibliographicCitation.startpage10671
local.bibliographicCitation.lastpage10676
local.identifier.doi10.1039/c7cp07562f
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciences
dc.date.updated2019-03-12T07:36:57Z
dcterms.accessRightsOpen Access
dc.provenancehttp://sherpa.ac.uk/romeo/issn/1463-9076/..."Author can archive pre-print (ie pre-refereeing). Author can archive post-print (ie final draft post-refereeing) with a 12 months embargo" (Sherpa/Romeo as of 7/5/2019)
CollectionsANU Research Publications

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