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Article: Ruthenium porphyrin catalyzed tandem sulfonium/ammonium ylide formation and [2,3]-sigmatropic rearrangement. A concise synthesis of (±)-platynecine
Title | Ruthenium porphyrin catalyzed tandem sulfonium/ammonium ylide formation and [2,3]-sigmatropic rearrangement. A concise synthesis of (±)-platynecine |
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Authors | |
Issue Date | 2004 |
Publisher | American 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? |
Abstract | meso-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 Identifier | http://hdl.handle.net/10722/168336 |
ISSN | 2023 Impact Factor: 3.3 2023 SCImago Journal Rankings: 0.724 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Zhou, CY | en_US |
dc.contributor.author | Yu, WY | en_US |
dc.contributor.author | Chan, PWH | en_US |
dc.contributor.author | Che, CM | en_US |
dc.date.accessioned | 2012-10-08T03:17:45Z | - |
dc.date.available | 2012-10-08T03:17:45Z | - |
dc.date.issued | 2004 | en_US |
dc.identifier.citation | Journal Of Organic Chemistry, 2004, v. 69 n. 21, p. 7072-7082 | en_US |
dc.identifier.issn | 0022-3263 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/168336 | - |
dc.description.abstract | meso-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.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/joc | en_US |
dc.relation.ispartof | Journal of Organic Chemistry | en_US |
dc.subject.mesh | Catalysis | en_US |
dc.subject.mesh | Heterocyclic Compounds, 2-Ring - Chemical Synthesis | en_US |
dc.subject.mesh | Molecular Structure | en_US |
dc.subject.mesh | Organometallic Compounds - Chemical Synthesis - Chemistry | en_US |
dc.subject.mesh | Porphyrins - Chemistry | en_US |
dc.subject.mesh | Quaternary Ammonium Compounds - Chemical Synthesis | en_US |
dc.subject.mesh | Ruthenium - Chemistry | en_US |
dc.subject.mesh | Stereoisomerism | en_US |
dc.subject.mesh | Sulfonium Compounds - Chemical Synthesis | en_US |
dc.title | Ruthenium porphyrin catalyzed tandem sulfonium/ammonium ylide formation and [2,3]-sigmatropic rearrangement. A concise synthesis of (±)-platynecine | en_US |
dc.type | Article | en_US |
dc.identifier.email | Zhou, CY:cyzhou@hku.hk | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Zhou, CY=rp00843 | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/jo049540v | en_US |
dc.identifier.pmid | 15471455 | - |
dc.identifier.scopus | eid_2-s2.0-5444256926 | en_US |
dc.identifier.hkuros | 98603 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-5444256926&selection=ref&src=s&origin=recordpage | en_US |
dc.identifier.volume | 69 | en_US |
dc.identifier.issue | 21 | en_US |
dc.identifier.spage | 7072 | en_US |
dc.identifier.epage | 7082 | en_US |
dc.identifier.isi | WOS:000224492000016 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Zhou, CY=35742480200 | en_US |
dc.identifier.scopusauthorid | Yu, WY=7403913673 | en_US |
dc.identifier.scopusauthorid | Chan, PWH=13607033800 | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.issnl | 0022-3263 | - |