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Article: Alkene cis-dihydroxylation by [(Me3tacn)(CF3CO2)RuVIO2]CIO4 (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane): Structural characterization of [3 + 2] cycloadducts and kinetic studies

TitleAlkene cis-dihydroxylation by [(Me3tacn)(CF3CO2)RuVIO2]CIO4 (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane): Structural characterization of [3 + 2] cycloadducts and kinetic studies
Authors
Issue Date2005
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html
Citation
Journal Of The American Chemical Society, 2005, v. 127 n. 41, p. 14239-14249 How to Cite?
Abstractcis-Dioxoruthenium(VI) complex [(Me3tacn)(CF3CO2)RuVIO2]CIO4 (1, Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) reacted with alkenes in aqueous tert-butyl alcohol to afford cis-1,2-diols in excellent yields under ambient conditions. When the reactions of 1 with alkenes were conducted in acetonitrile, oxidative C=C cleavage reaction prevailed giving carbonyl products in >90% yields without any cis-diol formation. The alkene cis-dihydroxylation and C=C cleavage reactions proceed via the formation of a [3 + 2] cycloadduct between 1 and alkenes, analogous to the related reactions with alkynes [Che et al. J. Am. Chem. Soc. 2000, 122, 11380], With cyclooctene and trans-β-methylstyrene as substrates, the Ru(III) cycloadducts [(Me3tacn)(CF 3CO2)RuIIIO(H)CH(CH2) 6HCO]CIO4 (4a) and [(Me3tacn)(CF 3CO2)RuIIIO(H)-PhCHCH(CH3)O]CIO 4 (4b) were isolated and structurally characterized by X-ray crystal analyses. The kinetics of the reactions of 1 with a series of p-substituted styrenes has been studied in acetonitrile by stopped-flow spectrophotometry. The second-order rate constants varied by 14-fold despite an overall span of 1.3 V for the one-electron oxidation potentials of alkenes. Secondary kinetic isotope effect (KIE) was observed for the oxidation of β-d2-styrene (kH/kD = 0.83 ± 0.04) and α-deuteriostyrene (kH/kD = 0.96 ± 0.03), which, together with the stereoselectivity of cis-alkene oxidation by 1, is in favor of a concerted mechanism. © 2005 American Chemical Society.
Persistent Identifierhttp://hdl.handle.net/10722/167960
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorYip, WPen_HK
dc.contributor.authorYu, WYen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:13:26Z-
dc.date.available2012-10-08T03:13:26Z-
dc.date.issued2005en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2005, v. 127 n. 41, p. 14239-14249en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167960-
dc.description.abstractcis-Dioxoruthenium(VI) complex [(Me3tacn)(CF3CO2)RuVIO2]CIO4 (1, Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane) reacted with alkenes in aqueous tert-butyl alcohol to afford cis-1,2-diols in excellent yields under ambient conditions. When the reactions of 1 with alkenes were conducted in acetonitrile, oxidative C=C cleavage reaction prevailed giving carbonyl products in >90% yields without any cis-diol formation. The alkene cis-dihydroxylation and C=C cleavage reactions proceed via the formation of a [3 + 2] cycloadduct between 1 and alkenes, analogous to the related reactions with alkynes [Che et al. J. Am. Chem. Soc. 2000, 122, 11380], With cyclooctene and trans-β-methylstyrene as substrates, the Ru(III) cycloadducts [(Me3tacn)(CF 3CO2)RuIIIO(H)CH(CH2) 6HCO]CIO4 (4a) and [(Me3tacn)(CF 3CO2)RuIIIO(H)-PhCHCH(CH3)O]CIO 4 (4b) were isolated and structurally characterized by X-ray crystal analyses. The kinetics of the reactions of 1 with a series of p-substituted styrenes has been studied in acetonitrile by stopped-flow spectrophotometry. The second-order rate constants varied by 14-fold despite an overall span of 1.3 V for the one-electron oxidation potentials of alkenes. Secondary kinetic isotope effect (KIE) was observed for the oxidation of β-d2-styrene (kH/kD = 0.83 ± 0.04) and α-deuteriostyrene (kH/kD = 0.96 ± 0.03), which, together with the stereoselectivity of cis-alkene oxidation by 1, is in favor of a concerted mechanism. © 2005 American Chemical Society.en_HK
dc.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.subject.meshAlkenes - Chemical Synthesis - Chemistryen_US
dc.subject.meshAza Compounds - Chemistryen_US
dc.subject.meshCrystallography, X-Rayen_US
dc.subject.meshCyclizationen_US
dc.subject.meshHydroxylationen_US
dc.subject.meshKineticsen_US
dc.subject.meshModels, Molecularen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshOrganometallic Compounds - Chemistryen_US
dc.subject.meshRuthenium - Chemistryen_US
dc.titleAlkene cis-dihydroxylation by [(Me3tacn)(CF3CO2)RuVIO2]CIO4 (Me3tacn = 1,4,7-trimethyl-1,4,7-triazacyclononane): Structural characterization of [3 + 2] cycloadducts and kinetic studiesen_HK
dc.typeArticleen_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja0528230en_HK
dc.identifier.pmid16218618-
dc.identifier.scopuseid_2-s2.0-26844562589en_HK
dc.identifier.hkuros117997-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-26844562589&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume127en_HK
dc.identifier.issue41en_HK
dc.identifier.spage14239en_HK
dc.identifier.epage14249en_HK
dc.identifier.isiWOS:000232605600047-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridYip, WP=8751048200en_HK
dc.identifier.scopusauthoridYu, WY=7403913673en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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