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Article: A density functional theory investigation of the Simmons-Smith cyclopropanation reaction: Examination of the insertion reaction of zinc into the C-I bond of CH2I2 and subsequent cyclopropanation reactions

TitleA density functional theory investigation of the Simmons-Smith cyclopropanation reaction: Examination of the insertion reaction of zinc into the C-I bond of CH2I2 and subsequent cyclopropanation reactions
Authors
Issue Date2002
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2002, v. 67 n. 1, p. 154-160 How to Cite?
AbstractThe insertion reaction of zinc into the C-I bond of CH 2I 2 and subsequent cyclopropanation reactions with CH 2CH 2 have been investigated using B3LYP level density functional theory calculations. The Simmons-Smith cyclopropanation reaction of olefins does not proceed easily due to the relatively large barriers on the insertion and cyclopropanation pathways. The computed results indicate that the IZnCH 2I molecule is the active reagent in the Simmons-Smith reaction. This is consistent with the IZnCH 2I reactive species being generated from diiodomethane and a Zn-Cu couple as proposed by several other research groups. The Simmons-Smith IZnCH 2I carbenoid and CH 2I-I carbenoid cyclopropanation reactions with olefins are compared. The reactions of olefins with the radicals from the decomposition of the IZnCH 2I and CH 2I-I species were also compared. We found that the chemical reactivity of the carbenoid species is dependent on its electrophilic behavior, steric effects, the leaving group character and the mechanism of the cyclopropanation reactions.
Persistent Identifierhttp://hdl.handle.net/10722/167746
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorFang, WHen_US
dc.contributor.authorPhillips, DLen_US
dc.contributor.authorWang, DQen_US
dc.contributor.authorLi, YLen_US
dc.date.accessioned2012-10-08T03:10:56Z-
dc.date.available2012-10-08T03:10:56Z-
dc.date.issued2002en_US
dc.identifier.citationJournal Of Organic Chemistry, 2002, v. 67 n. 1, p. 154-160en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/167746-
dc.description.abstractThe insertion reaction of zinc into the C-I bond of CH 2I 2 and subsequent cyclopropanation reactions with CH 2CH 2 have been investigated using B3LYP level density functional theory calculations. The Simmons-Smith cyclopropanation reaction of olefins does not proceed easily due to the relatively large barriers on the insertion and cyclopropanation pathways. The computed results indicate that the IZnCH 2I molecule is the active reagent in the Simmons-Smith reaction. This is consistent with the IZnCH 2I reactive species being generated from diiodomethane and a Zn-Cu couple as proposed by several other research groups. The Simmons-Smith IZnCH 2I carbenoid and CH 2I-I carbenoid cyclopropanation reactions with olefins are compared. The reactions of olefins with the radicals from the decomposition of the IZnCH 2I and CH 2I-I species were also compared. We found that the chemical reactivity of the carbenoid species is dependent on its electrophilic behavior, steric effects, the leaving group character and the mechanism of the cyclopropanation reactions.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.meshCyclizationen_US
dc.subject.meshCyclopropanes - Chemical Synthesisen_US
dc.subject.meshHydrocarbons, Iodinated - Chemistryen_US
dc.subject.meshModels, Chemicalen_US
dc.subject.meshThermodynamicsen_US
dc.subject.meshZinc - Chemistryen_US
dc.titleA density functional theory investigation of the Simmons-Smith cyclopropanation reaction: Examination of the insertion reaction of zinc into the C-I bond of CH2I2 and subsequent cyclopropanation reactionsen_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/jo0107655en_US
dc.identifier.pmid11777453-
dc.identifier.scopuseid_2-s2.0-0037059475en_US
dc.identifier.hkuros73874-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037059475&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume67en_US
dc.identifier.issue1en_US
dc.identifier.spage154en_US
dc.identifier.epage160en_US
dc.identifier.isiWOS:000173151200024-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridFang, WH=7202236871en_US
dc.identifier.scopusauthoridPhillips, DL=7404519365en_US
dc.identifier.scopusauthoridWang, DQ=7407071795en_US
dc.identifier.scopusauthoridLi, YL=27168456500en_US

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