Please use this identifier to cite or link to this item: https://hdl.handle.net/1959.11/9303
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dc.contributor.authorGlover, Stephenen
dc.contributor.authorWhite, Jonathan Men
dc.contributor.authorRosser, Adam Andrewen
dc.contributor.authorDigianantonio, Katherine Men
dc.date.accessioned2012-01-25T11:52:00Z-
dc.date.issued2011-
dc.identifier.citationThe Journal of Organic Chemistry, 76(23), p. 9757-9763en
dc.identifier.issn1520-6904en
dc.identifier.issn0022-3263en
dc.identifier.urihttps://hdl.handle.net/1959.11/9303-
dc.description.abstractThe first X-ray structures of two anomeric N,N-dialkoxyamides (2 and 3) have been obtained, which confirm that they are highly pyramidalized at nitrogen and have long N-CO bonds, a characteristic of other anomeric amides and a consequence of drastically reduced amidicity. The crystals also demonstrate chirality at the amide nitrogen in the solid state. The structures are well-predicted by density functional calculations using N,N-dimethoxyacetamide as a model. The amidicity of N,N-dimethoxyacetamide has been estimated by two independent methods, COSNAR and a new transamidation method, which give almost identical resonance stabilization energies of -8.6 kcal mol⁻¹ and only 47% that of N,N-dimethylacetamide computed at the same level. The total destabilization is composed of a resonance and an inductive contribution, which we have evaluated separately. The electronegative oxygens at nitrogen are responsible for localization of the nitrogen lone pair on the amide nitrogen, a factor that contributes to a loss of resonance over and above the impact of pyramidalization at nitrogen, as well as the fact that N,N-dimethoxyacetamide is predicted to protonate on the carbonyl oxygen in preference to nitrogen.en
dc.languageenen
dc.publisherAmerican Chemical Societyen
dc.relation.ispartofThe Journal of Organic Chemistryen
dc.titleStructures of N,N-Dialkoxyamides: Pyramidal Anomeric Amides with Low Amidicityen
dc.typeJournal Articleen
dc.identifier.doi10.1021/jo201856uen
dc.subject.keywordsStructural Chemistry and Spectroscopyen
dc.subject.keywordsTheoretical and Computational Chemistryen
dc.subject.keywordsPhysical Organic Chemistryen
local.contributor.firstnameStephenen
local.contributor.firstnameJonathan Men
local.contributor.firstnameAdam Andrewen
local.contributor.firstnameKatherine Men
local.subject.for2008030799 Theoretical and Computational Chemistry not elsewhere classifieden
local.subject.for2008030606 Structural Chemistry and Spectroscopyen
local.subject.for2008030505 Physical Organic Chemistryen
local.subject.seo2008970103 Expanding Knowledge in the Chemical Sciencesen
local.profile.schoolSchool of Science and Technologyen
local.profile.schoolChemistryen
local.profile.schoolSchool of Science and Technologyen
local.profile.schoolChemistryen
local.profile.emailsglover@une.edu.auen
local.profile.emailwhitejm@unimelb.edu.auen
local.profile.emailarosser3@une.edu.auen
local.profile.emailkdigiana@princeton.eduen
local.output.categoryC1en
local.record.placeauen
local.record.institutionUniversity of New Englanden
local.identifier.epublicationsrecordune-20111116-082313en
local.publisher.placeUnited States of Americaen
local.format.startpage9757en
local.format.endpage9763en
local.identifier.scopusid82255170733en
local.peerreviewedYesen
local.identifier.volume76en
local.identifier.issue23en
local.title.subtitlePyramidal Anomeric Amides with Low Amidicityen
local.contributor.lastnameGloveren
local.contributor.lastnameWhiteen
local.contributor.lastnameRosseren
local.contributor.lastnameDigianantonioen
dc.identifier.staffune-id:sgloveren
dc.identifier.staffune-id:arosser3en
local.profile.orcid0000-0002-9344-8669en
local.profile.orcid0000-0002-4123-7704en
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.profile.roleauthoren
local.identifier.unepublicationidune:9494en
dc.identifier.academiclevelAcademicen
dc.identifier.academiclevelAcademicen
local.title.maintitleStructures of N,N-Dialkoxyamidesen
local.output.categorydescriptionC1 Refereed Article in a Scholarly Journalen
local.search.authorGlover, Stephenen
local.search.authorWhite, Jonathan Men
local.search.authorRosser, Adam Andrewen
local.search.authorDigianantonio, Katherine Men
local.uneassociationUnknownen
local.identifier.wosid000297274800023en
local.year.published2011en
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