File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: A density functional theory study of the 5-exo cyclization reactions of α-substituted 6,6-diphenyl-5-hexenyl radicals

TitleA density functional theory study of the 5-exo cyclization reactions of α-substituted 6,6-diphenyl-5-hexenyl radicals
Authors
Issue Date2006
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2006, v. 71 n. 5, p. 1984-1988 How to Cite?
AbstractDensity functional theory computations were done to study the 5-exo radical cyclization reactions of α-substituted 6,6-diphenyl-5-hexenyl radicals. The methoxy electron donor group substitution reduced the barrier to reaction by about 0.5 kcal/mol. On the other hand, the electron acceptor group substitutions (ethoxycarbonyl, carboxylic acid, carboxylate, and cyano) raised the barrier to reaction by varying amounts (0.5-2.1 kcal /mol). The entropic terms of these cyclization reactions are briefly discussed. Solvent effects on these reactions were explored by calculations that included a polarizable continuum model for the solvent. The density functional theory calculated results were found to be in good agreement with the experimental data available in the literature and help to explain some of the observed variation in these types of cyclization reactions with various substitutions. Our results also provide an explanation for why the rate constant for the carboxylate group substituted radical was found to be an order of magnitude smaller than the rate constant for those radicals with carboxylic acid and ethoxycarbonyl substitutions. © 2006 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168007
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorGuan, Xen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorYang, Den_US
dc.date.accessioned2012-10-08T03:14:01Z-
dc.date.available2012-10-08T03:14:01Z-
dc.date.issued2006en_US
dc.identifier.citationJournal Of Organic Chemistry, 2006, v. 71 n. 5, p. 1984-1988en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/168007-
dc.description.abstractDensity functional theory computations were done to study the 5-exo radical cyclization reactions of α-substituted 6,6-diphenyl-5-hexenyl radicals. The methoxy electron donor group substitution reduced the barrier to reaction by about 0.5 kcal/mol. On the other hand, the electron acceptor group substitutions (ethoxycarbonyl, carboxylic acid, carboxylate, and cyano) raised the barrier to reaction by varying amounts (0.5-2.1 kcal /mol). The entropic terms of these cyclization reactions are briefly discussed. Solvent effects on these reactions were explored by calculations that included a polarizable continuum model for the solvent. The density functional theory calculated results were found to be in good agreement with the experimental data available in the literature and help to explain some of the observed variation in these types of cyclization reactions with various substitutions. Our results also provide an explanation for why the rate constant for the carboxylate group substituted radical was found to be an order of magnitude smaller than the rate constant for those radicals with carboxylic acid and ethoxycarbonyl substitutions. © 2006 American Chemical Society.en_US
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jocen_US
dc.relation.ispartofJournal of Organic Chemistryen_US
dc.titleA density functional theory study of the 5-exo cyclization reactions of α-substituted 6,6-diphenyl-5-hexenyl radicalsen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.emailYang, D:yangdan@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.identifier.authorityYang, D=rp00825en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jo052328men_US
dc.identifier.pmid16496984-
dc.identifier.scopuseid_2-s2.0-33644641632en_US
dc.identifier.hkuros119094-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-33644641632&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume71en_US
dc.identifier.issue5en_US
dc.identifier.spage1984en_US
dc.identifier.epage1988en_US
dc.identifier.isiWOS:000235896800027-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridGuan, X=8313149700en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridYang, D=7404800756en_US

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats