File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Density functional theory studies of negishi alkyl-alkyl cross-coupling reactions catalyzed by a methylterpyridyl-Ni(I) complex

TitleDensity functional theory studies of negishi alkyl-alkyl cross-coupling reactions catalyzed by a methylterpyridyl-Ni(I) complex
Authors
Issue Date2008
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2008, v. 73 n. 10, p. 3680-3688 How to Cite?
Abstract(Graph Presented) Density functional theory calculations were done to examine the potential energy surfaces of Ni(I)-catalyzed Negishi alkyl-alkyl cross-coupling reactions by using propyl iodide and isopropyl iodide as model alkyl electrophiles and CH3ZnI as a model alkyl nucleophile. A four-step catalytic cycle involving iodine transfer, radical addition, reductive elimination, and transmetalation steps were characterized structurally and energetically. The reaction mechanism for this catalytic cycle appears feasible based on the calculated free energy profiles for the reactions. The iodine transfer step is the rate-determining step for the Ni(tpy)-CH3 (tpy = 2,2′6′,2″-terpyridine) reactions with alkyl iodides. For secondary alkyl electrophiles, the oxidative addition intermediate, Ni(III), prefers to undergo decomposition over reductive elimination, whereas for the primary alkyl electrophiles, Ni(III) prefers to undergo reductive elimination over decomposition based on comparison of the relative reaction rates for these two types of steps. In addition, thermodynamic data were employed to help explain why the yield of the coupled product is very low from the Ni(II)-alkyl halide reactions with organozinc reagents. © 2008 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/68838
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLin, Xen_HK
dc.contributor.authorPhillips, DLen_HK
dc.date.accessioned2010-09-06T06:08:11Z-
dc.date.available2010-09-06T06:08:11Z-
dc.date.issued2008en_HK
dc.identifier.citationJournal Of Organic Chemistry, 2008, v. 73 n. 10, p. 3680-3688en_HK
dc.identifier.issn0022-3263en_HK
dc.identifier.urihttp://hdl.handle.net/10722/68838-
dc.description.abstract(Graph Presented) Density functional theory calculations were done to examine the potential energy surfaces of Ni(I)-catalyzed Negishi alkyl-alkyl cross-coupling reactions by using propyl iodide and isopropyl iodide as model alkyl electrophiles and CH3ZnI as a model alkyl nucleophile. A four-step catalytic cycle involving iodine transfer, radical addition, reductive elimination, and transmetalation steps were characterized structurally and energetically. The reaction mechanism for this catalytic cycle appears feasible based on the calculated free energy profiles for the reactions. The iodine transfer step is the rate-determining step for the Ni(tpy)-CH3 (tpy = 2,2′6′,2″-terpyridine) reactions with alkyl iodides. For secondary alkyl electrophiles, the oxidative addition intermediate, Ni(III), prefers to undergo decomposition over reductive elimination, whereas for the primary alkyl electrophiles, Ni(III) prefers to undergo reductive elimination over decomposition based on comparison of the relative reaction rates for these two types of steps. In addition, thermodynamic data were employed to help explain why the yield of the coupled product is very low from the Ni(II)-alkyl halide reactions with organozinc reagents. © 2008 American Chemical Society.en_HK
dc.languageengen_HK
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/jocen_HK
dc.relation.ispartofJournal of Organic Chemistryen_HK
dc.titleDensity functional theory studies of negishi alkyl-alkyl cross-coupling reactions catalyzed by a methylterpyridyl-Ni(I) complexen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0022-3263&volume=73&spage=3680&epage=3688&date=2008&atitle=Density+Functional+Theory+Studies+of+Negishi+Alkyl-Alkyl+Cross-Coupling+Reactions+Catalyzed+by+a+Methylterpyridyl-Ni(I)+Complex+en_HK
dc.identifier.emailPhillips, DL:phillips@hku.hken_HK
dc.identifier.authorityPhillips, DL=rp00770en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/jo702497pen_HK
dc.identifier.pmid18410144-
dc.identifier.scopuseid_2-s2.0-43449114195en_HK
dc.identifier.hkuros151586en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-43449114195&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume73en_HK
dc.identifier.issue10en_HK
dc.identifier.spage3680en_HK
dc.identifier.epage3688en_HK
dc.identifier.isiWOS:000255698500003-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridLin, X=35205535200en_HK
dc.identifier.scopusauthoridPhillips, DL=7404519365en_HK

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats