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Article: Concurrent cyclopropanation by carbenes and carbanions? A density functional theory study on the reaction pathways

TitleConcurrent cyclopropanation by carbenes and carbanions? A density functional theory study on the reaction pathways
Authors
Issue Date2007
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2007, v. 72 n. 14, p. 5139-5145 How to Cite?
Abstract(Chemical Equation Presented) The mechanisms for the addition reactions of phenylhalocarbenes and phenyldihalomethide carbanions with acrylonitrile (ACN) and trimethylethylene (TME) have been investigated using an ab initio BH and HLYP/6-31G (d, p) level of theory. Solvent effects on these reactions have been explored by calculations that included a polarizable continuum model (PCM) for the solvent (THF). These model calculations show that for the addition of phenylhalocarbenes, a TME species may readily undergo addition reactions with carbenes while ACN has a high-energy barrier to overcome. It was also found that phenyldihalomethide carbanions do not readily add to the electron-rich TME. The cyclopropane yields only appear to occur via addition of PhCBr to TME. However, the cyclopropanation proceeds not only via slow addition of phenylhalocarbenes to ACN but also forms through the stepwise reaction of phenyldihalomethide carbanions with ACN. Our calculation results are in good agreement with experimental observations (Moss, R.A.; Tian, J.-Z. J. Am. Chem. Soc. 2005, 127, 8960) that indicate that the cyclopropanation of phenylhalocarbenes and phenyldihalomethide carbanions with ACN are concurrent in THF. © 2007 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/168127
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorFang, Ren_US
dc.contributor.authorKe, Zen_US
dc.contributor.authorShen, Yen_US
dc.contributor.authorZhao, Cen_US
dc.contributor.authorPhillips, DLen_US
dc.date.accessioned2012-10-08T03:15:25Z-
dc.date.available2012-10-08T03:15:25Z-
dc.date.issued2007en_US
dc.identifier.citationJournal Of Organic Chemistry, 2007, v. 72 n. 14, p. 5139-5145en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/168127-
dc.description.abstract(Chemical Equation Presented) The mechanisms for the addition reactions of phenylhalocarbenes and phenyldihalomethide carbanions with acrylonitrile (ACN) and trimethylethylene (TME) have been investigated using an ab initio BH and HLYP/6-31G (d, p) level of theory. Solvent effects on these reactions have been explored by calculations that included a polarizable continuum model (PCM) for the solvent (THF). These model calculations show that for the addition of phenylhalocarbenes, a TME species may readily undergo addition reactions with carbenes while ACN has a high-energy barrier to overcome. It was also found that phenyldihalomethide carbanions do not readily add to the electron-rich TME. The cyclopropane yields only appear to occur via addition of PhCBr to TME. However, the cyclopropanation proceeds not only via slow addition of phenylhalocarbenes to ACN but also forms through the stepwise reaction of phenyldihalomethide carbanions with ACN. Our calculation results are in good agreement with experimental observations (Moss, R.A.; Tian, J.-Z. J. Am. Chem. Soc. 2005, 127, 8960) that indicate that the cyclopropanation of phenylhalocarbenes and phenyldihalomethide carbanions with ACN are concurrent in THF. © 2007 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.subject.meshCyclopropanes - Chemistryen_US
dc.subject.meshHalogens - Chemistryen_US
dc.subject.meshHydrocarbons - Chemistryen_US
dc.subject.meshMethane - Analogs & Derivatives - Chemistryen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshMolecular Conformationen_US
dc.titleConcurrent cyclopropanation by carbenes and carbanions? A density functional theory study on the reaction pathwaysen_US
dc.typeArticleen_US
dc.identifier.emailPhillips, DL:phillips@hku.hken_US
dc.identifier.authorityPhillips, DL=rp00770en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jo0704356en_US
dc.identifier.pmid17552566-
dc.identifier.scopuseid_2-s2.0-34447300964en_US
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-34447300964&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume72en_US
dc.identifier.issue14en_US
dc.identifier.spage5139en_US
dc.identifier.epage5145en_US
dc.identifier.isiWOS:000247612200014-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridFang, R=10144173000en_US
dc.identifier.scopusauthoridKe, Z=14048262500en_US
dc.identifier.scopusauthoridShen, Y=7404767215en_US
dc.identifier.scopusauthoridZhao, C=7403563836en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US

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