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Article: Ruthenium porphyrin catalyzed tandem sulfonium/ammonium ylide formation and [2,3]-sigmatropic rearrangement. A concise synthesis of (±)-platynecine

TitleRuthenium porphyrin catalyzed tandem sulfonium/ammonium ylide formation and [2,3]-sigmatropic rearrangement. A concise synthesis of (±)-platynecine
Authors
Issue Date2004
PublisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc
Citation
Journal Of Organic Chemistry, 2004, v. 69 n. 21, p. 7072-7082 How to Cite?
Abstractmeso-Tetrakis(p-tolyl)porphyrinatoruthenium(II) carbonyl, [Ru II(TTP)(CO)], can effect intermolecular sulfonium and ammonium ylide formation by catalytic decomposition of diazo compounds such as ethyl diazoacetate (EDA) in the presence of allyl sulfides and amines. Exclusive formation of [2,3]-sigmatropic rearrangement products (70-80% yields) was observed without [1,2]-rearrangement products being detected. The Ru-catalyzed reaction of EDA with disubstituted allyl sulfides such as crotyl sulfide produced an equimolar mixture of anti- and syn-2-(ethylthio)-3-methyl-4- pentenoic acid ethyl ester. The analogous "EDA + N,N- dimethylcrotylamine" reaction afforded a mixture of anti- and syn-2-(N,N-dimethylamino)-3-methyl-4-pentenoic acid ethyl esters with a diastereoselectivity of 3:1. The observed catalytic activity of [Ru II(TTP)(CO)] for the ylide [2,3]-sigmatropic rearrangement is comparable to the reported examples involving [Rh2(CH 3CO2)4] and [Cu(acac)2] as catalyst. Similarly, cyclic sulfonium and ammonium ylides can be produced by intramolecular reaction of a diazo group tethered to allyl sulfides and amines under the [RuII-(TTP)(CO)]-catalyzed reaction conditions. The subsequent [2,3]-sigmatropic rearrangement of the cyclic ylides furnished 2-allyl-substituted sulfur and nitrogen heterocycles in good yields (>90%). By employing [RuII(TTP)(CO)] as catalyst, the cyclic ammonium ylide [2,3]-sigmatropic rearrangement reaction was successfully applied for the total synthesis of (±)-platynecine starting from cis-2-butenediol.
Persistent Identifierhttp://hdl.handle.net/10722/168336
ISSN
2015 Impact Factor: 4.785
2015 SCImago Journal Rankings: 2.095
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorZhou, CYen_US
dc.contributor.authorYu, WYen_US
dc.contributor.authorChan, PWHen_US
dc.contributor.authorChe, CMen_US
dc.date.accessioned2012-10-08T03:17:45Z-
dc.date.available2012-10-08T03:17:45Z-
dc.date.issued2004en_US
dc.identifier.citationJournal Of Organic Chemistry, 2004, v. 69 n. 21, p. 7072-7082en_US
dc.identifier.issn0022-3263en_US
dc.identifier.urihttp://hdl.handle.net/10722/168336-
dc.description.abstractmeso-Tetrakis(p-tolyl)porphyrinatoruthenium(II) carbonyl, [Ru II(TTP)(CO)], can effect intermolecular sulfonium and ammonium ylide formation by catalytic decomposition of diazo compounds such as ethyl diazoacetate (EDA) in the presence of allyl sulfides and amines. Exclusive formation of [2,3]-sigmatropic rearrangement products (70-80% yields) was observed without [1,2]-rearrangement products being detected. The Ru-catalyzed reaction of EDA with disubstituted allyl sulfides such as crotyl sulfide produced an equimolar mixture of anti- and syn-2-(ethylthio)-3-methyl-4- pentenoic acid ethyl ester. The analogous "EDA + N,N- dimethylcrotylamine" reaction afforded a mixture of anti- and syn-2-(N,N-dimethylamino)-3-methyl-4-pentenoic acid ethyl esters with a diastereoselectivity of 3:1. The observed catalytic activity of [Ru II(TTP)(CO)] for the ylide [2,3]-sigmatropic rearrangement is comparable to the reported examples involving [Rh2(CH 3CO2)4] and [Cu(acac)2] as catalyst. Similarly, cyclic sulfonium and ammonium ylides can be produced by intramolecular reaction of a diazo group tethered to allyl sulfides and amines under the [RuII-(TTP)(CO)]-catalyzed reaction conditions. The subsequent [2,3]-sigmatropic rearrangement of the cyclic ylides furnished 2-allyl-substituted sulfur and nitrogen heterocycles in good yields (>90%). By employing [RuII(TTP)(CO)] as catalyst, the cyclic ammonium ylide [2,3]-sigmatropic rearrangement reaction was successfully applied for the total synthesis of (±)-platynecine starting from cis-2-butenediol.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.meshCatalysisen_US
dc.subject.meshHeterocyclic Compounds, 2-Ring - Chemical Synthesisen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshOrganometallic Compounds - Chemical Synthesis - Chemistryen_US
dc.subject.meshPorphyrins - Chemistryen_US
dc.subject.meshQuaternary Ammonium Compounds - Chemical Synthesisen_US
dc.subject.meshRuthenium - Chemistryen_US
dc.subject.meshStereoisomerismen_US
dc.subject.meshSulfonium Compounds - Chemical Synthesisen_US
dc.titleRuthenium porphyrin catalyzed tandem sulfonium/ammonium ylide formation and [2,3]-sigmatropic rearrangement. A concise synthesis of (±)-platynecineen_US
dc.typeArticleen_US
dc.identifier.emailZhou, CY:cyzhou@hku.hken_US
dc.identifier.emailChe, CM:cmche@hku.hken_US
dc.identifier.authorityZhou, CY=rp00843en_US
dc.identifier.authorityChe, CM=rp00670en_US
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/jo049540ven_US
dc.identifier.pmid15471455-
dc.identifier.scopuseid_2-s2.0-5444256926en_US
dc.identifier.hkuros98603-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-5444256926&selection=ref&src=s&origin=recordpageen_US
dc.identifier.volume69en_US
dc.identifier.issue21en_US
dc.identifier.spage7072en_US
dc.identifier.epage7082en_US
dc.identifier.isiWOS:000224492000016-
dc.publisher.placeUnited Statesen_US
dc.identifier.scopusauthoridZhou, CY=35742480200en_US
dc.identifier.scopusauthoridYu, WY=7403913673en_US
dc.identifier.scopusauthoridChan, PWH=13607033800en_US
dc.identifier.scopusauthoridChe, CM=7102442791en_US

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