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Article: Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: Aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins

TitleMetalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: Aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins
Authors
KeywordsAmidation
Asymmetric
Aziridination
Catalysis
Manganese
Porphyrinoids
Ruthenium
Issue Date2002
PublisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistry
Citation
Chemistry - A European Journal, 2002, v. 8 n. 7, p. 1563-1572 How to Cite?
AbstractChiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*) (CO)(EtOH))] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99% substrate conversions and up to 94% aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32% and amide selectivities of up to 91%. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)2" + NH2SO2Me", affording the N-substituted methanesulfonamides in up to 56% ee with substrate conversions of up to 34% and amide selectivities of up to 92%. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)2 + NH2R (R = Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49% and amide selectivities of up to 90% (α:β ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis-(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)2] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2-(4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5 × 10-3 dm3mol-1 s-1. An X-ray structure determination of complex 4 reveals an O- rather than N-coordination of the aziridine axial ligand. The fact that the N-tosylaziridine in 4 does not adopt an N-coordination mode disfavors a concerted pathway in the aziridination by a tosylimido ruthenium porphyrin active species.
Persistent Identifierhttp://hdl.handle.net/10722/167741
ISSN
2015 Impact Factor: 5.771
2015 SCImago Journal Rankings: 2.323
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorLiang, JLen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorYu, XQen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:10:50Z-
dc.date.available2012-10-08T03:10:50Z-
dc.date.issued2002en_HK
dc.identifier.citationChemistry - A European Journal, 2002, v. 8 n. 7, p. 1563-1572en_HK
dc.identifier.issn0947-6539en_HK
dc.identifier.urihttp://hdl.handle.net/10722/167741-
dc.description.abstractChiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*) (CO)(EtOH))] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99% substrate conversions and up to 94% aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32% and amide selectivities of up to 91%. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)2" + NH2SO2Me", affording the N-substituted methanesulfonamides in up to 56% ee with substrate conversions of up to 34% and amide selectivities of up to 92%. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)2 + NH2R (R = Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49% and amide selectivities of up to 90% (α:β ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis-(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)2] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2-(4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5 × 10-3 dm3mol-1 s-1. An X-ray structure determination of complex 4 reveals an O- rather than N-coordination of the aziridine axial ligand. The fact that the N-tosylaziridine in 4 does not adopt an N-coordination mode disfavors a concerted pathway in the aziridination by a tosylimido ruthenium porphyrin active species.en_HK
dc.languageengen_US
dc.publisherWiley - V C H Verlag GmbH & Co KGaA. The Journal's web site is located at http://www.wiley-vch.de/home/chemistryen_HK
dc.relation.ispartofChemistry - A European Journalen_HK
dc.subjectAmidationen_HK
dc.subjectAsymmetricen_HK
dc.subjectAziridinationen_HK
dc.subjectCatalysisen_HK
dc.subjectManganeseen_HK
dc.subjectPorphyrinoidsen_HK
dc.subjectRutheniumen_HK
dc.titleMetalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: Aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrinsen_HK
dc.typeArticleen_HK
dc.identifier.emailHuang, JS: jshuang@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1002/1521-3765(20020402)8:7<1563::AID-CHEM1563>3.0.CO;2-Ven_HK
dc.identifier.pmid11933085-
dc.identifier.scopuseid_2-s2.0-0037006869en_HK
dc.identifier.hkuros69079-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0037006869&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume8en_HK
dc.identifier.issue7en_HK
dc.identifier.spage1563en_HK
dc.identifier.epage1572en_HK
dc.identifier.isiWOS:000174843500009-
dc.publisher.placeGermanyen_HK
dc.identifier.scopusauthoridLiang, JL=7404541484en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridYu, XQ=7404115847en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

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