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Article: Chemoselective Oxidation of Alcohols to Aldehydes and Ketones by tert -Butyl Hydroperoxide Catalyzed by a Ruthenium Complex of N,N′,N″-Trimethyl-1,4,7-triazacyclononane

TitleChemoselective Oxidation of Alcohols to Aldehydes and Ketones by tert -Butyl Hydroperoxide Catalyzed by a Ruthenium Complex of N,N′,N″-Trimethyl-1,4,7-triazacyclononane
Authors
Issue Date1998
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 1998, v. 63 n. 9, p. 2873-2877 How to Cite?
AbstractAn operationally simple method based on [Cn*RuIII(CF3CO2) 3·H2O] (Cn* = N,N′,N″-trimethyl-1,4,7-triazacyclononane) catalyst and 1-1.2 equiv of tert-butyl hydroperoxide as terminal oxidant is effective for selective transformation of alcohols to aldehydes and ketones in methylene chloride. The reaction proceeds in high yield and selectivity. Preparation of benzaldehyde (98% yield) from benzyl alcohol on a 200 mmol scale can be performed without modification of the procedure such as slow addition of the oxidant or cooling to 0°C, and catalyst turnovers of 700 are achieved. Oxidation of geraniol which contains an isolated trisubstituted C=C bond leads to geranial selectively without oxidation of the C=C bond. Results from Hammett correlation studies (ρ = -0.47) and primary kinetic isotope effect (kH/kD = 4.8) for the catalytic benzyl alcohol oxidations are inconsistent with an oxoruthenium (O=Ru) based mechanism. A mechanism involving reactive tBuO·/tBuOO· radicals is also excluded based on results from previous works: Cheng, W.-C.; Fung, W.-H.; Che, C.-M. J. Mol. Catal. (A) 1996, 113, 311; absence of di-tert-butyl peroxide; and using cumyl hydroperoxide as a radical probe. A tert-butylperoxoruthenium complex is postulated to be the active intermediate.
Persistent Identifierhttp://hdl.handle.net/10722/167347
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorFung, WHen_US
dc.contributor.authorYu, WYen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:05:54Z-
dc.date.available2012-10-08T03:05:54Z-
dc.date.issued1998en_US
dc.identifier.citationJournal Of Organic Chemistry, 1998, v. 63 n. 9, p. 2873-2877en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/167347-
dc.description.abstractAn operationally simple method based on [Cn*RuIII(CF3CO2) 3·H2O] (Cn* = N,N′,N″-trimethyl-1,4,7-triazacyclononane) catalyst and 1-1.2 equiv of tert-butyl hydroperoxide as terminal oxidant is effective for selective transformation of alcohols to aldehydes and ketones in methylene chloride. The reaction proceeds in high yield and selectivity. Preparation of benzaldehyde (98% yield) from benzyl alcohol on a 200 mmol scale can be performed without modification of the procedure such as slow addition of the oxidant or cooling to 0°C, and catalyst turnovers of 700 are achieved. Oxidation of geraniol which contains an isolated trisubstituted C=C bond leads to geranial selectively without oxidation of the C=C bond. Results from Hammett correlation studies (ρ = -0.47) and primary kinetic isotope effect (kH/kD = 4.8) for the catalytic benzyl alcohol oxidations are inconsistent with an oxoruthenium (O=Ru) based mechanism. A mechanism involving reactive tBuO·/tBuOO· radicals is also excluded based on results from previous works: Cheng, W.-C.; Fung, W.-H.; Che, C.-M. J. Mol. Catal. (A) 1996, 113, 311; absence of di-tert-butyl peroxide; and using cumyl hydroperoxide as a radical probe. A tert-butylperoxoruthenium complex is postulated to be the active intermediate.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.titleChemoselective Oxidation of Alcohols to Aldehydes and Ketones by tert -Butyl Hydroperoxide Catalyzed by a Ruthenium Complex of N,N′,N″-Trimethyl-1,4,7-triazacyclononaneen_US
dc.typeArticleen_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jo971892x-
dc.identifier.scopuseid_2-s2.0-0001472321en_US
dc.identifier.hkuros32041-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0001472321&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume63en_US
dc.identifier.issue9en_US
dc.identifier.spage2873en_US
dc.identifier.epage2877en_US
dc.identifier.isiWOS:000073505600024-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridFung, WH=7102150303en_US
dc.identifier.scopusauthoridYu, WY=7403913673en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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