DC Field | Value | Language |
---|---|---|
dc.contributor.author | Lee, JM | ko |
dc.contributor.author | Ahn, DS | ko |
dc.contributor.author | Jung, DY | ko |
dc.contributor.author | Lee, J | ko |
dc.contributor.author | Do, Youngkyu | ko |
dc.contributor.author | Kim, Sangkyu | ko |
dc.contributor.author | Chang, Sukbok | ko |
dc.date.accessioned | 2009-08-27T05:43:40Z | - |
dc.date.available | 2009-08-27T05:43:40Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 2006-10 | - |
dc.identifier.citation | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.128, no.39, pp.12954 - 12962 | - |
dc.identifier.issn | 0002-7863 | - |
dc.identifier.uri | http://hdl.handle.net/10203/10826 | - |
dc.description.abstract | An efficient procedure for the preparation of Z-enamides has been developed, involving the reaction of primary amides with conjugated olefins using a Pd/Cu cocatalyst system. It was found that certain additives, such as phosphine oxides and phosphonates, increase the efficiency of the reaction in nonpolar solvents under an oxygen atmosphere, thus producing a variety of Z-enamides in high yields with excellent stereoselectivity under Wacker-type conditions. The oxidative amidation reaction has a broad substrate scope, allowing alkyl, aryl, and vinyl amides to react with olefins conjugated with ester, amide, phosphonate, and ketone groups. The notable preference for the formation of Z-enamides is presumably due to the presence of an intramolecular hydrogen bond between the amido proton and the carbonyl oxygen. The energy difference between two plausible sigma-alkylamidopalladium intermediates, leading to Z- and E-isomeric enamide products, respectively, was calculated to be 4.18 kcal/mol. The beta-hydride elimination step is assumed to be a stereochemistry-determining step in the overall oxidative amidation process, with the energy level for the transition state leading to the Z- enamide being 5.35 kcal/mol lower than that leading to the E-isomer. The efficiency of photoisomerization between Z- and E-enamides was observed to be largely dependent on the substrates' substituents, and certain E-enamides could be obtained in synthetically useful yields by photoirradiation of Z- isomers. Synthetic application of the present method was successfully demonstrated by a direct formal synthesis of cis-CJ-15,801. | - |
dc.description.sponsorship | This paper is dedicated to Professor Sunggak Kim on the occasion of his 60th birthday. This research was supported by the Center for Molecular Design and Synthesis (CMDS) at KAIST and grant no. R01-2005-000-10381-0 from the Basic Research Program and Korea Science and Engineering Foundation (no. R01-2005-000-10117-0). | en |
dc.language | English | - |
dc.language.iso | en_US | en |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | CROSS-COUPLING REACTIONS | - |
dc.subject | DIELS-ALDER REACTIONS | - |
dc.subject | BETA-HYDRIDE ELIMINATION | - |
dc.subject | ASYMMETRIC CATALYSIS | - |
dc.subject | ENANTIOSELECTIVE HYDROGENATION | - |
dc.subject | AEROBIC OXIDATION | - |
dc.subject | MOLECULAR-OXYGEN | - |
dc.subject | PALLADIUM(II)-CATALYZED CYCLIZATION | - |
dc.subject | BIOLOGICAL-PROPERTIES | - |
dc.subject | VINYLIC SUBSTITUTION | - |
dc.title | Hydrogen-bond-directed highly stereoselective synthesis of Z-enamides via Pd-catalyzed oxidative amidation of conjugated olefins | - |
dc.type | Article | - |
dc.identifier.wosid | 000240795000073 | - |
dc.identifier.scopusid | 2-s2.0-33749531743 | - |
dc.type.rims | ART | - |
dc.citation.volume | 128 | - |
dc.citation.issue | 39 | - |
dc.citation.beginningpage | 12954 | - |
dc.citation.endingpage | 12962 | - |
dc.citation.publicationname | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | - |
dc.identifier.doi | 10.1021/ja0639315 | - |
dc.embargo.liftdate | 9999-12-31 | - |
dc.embargo.terms | 9999-12-31 | - |
dc.contributor.localauthor | Do, Youngkyu | - |
dc.contributor.localauthor | Kim, Sangkyu | - |
dc.contributor.localauthor | Chang, Sukbok | - |
dc.contributor.nonIdAuthor | Lee, JM | - |
dc.contributor.nonIdAuthor | Ahn, DS | - |
dc.contributor.nonIdAuthor | Jung, DY | - |
dc.contributor.nonIdAuthor | Lee, J | - |
dc.type.journalArticle | Review | - |
dc.subject.keywordPlus | CROSS-COUPLING REACTIONS | - |
dc.subject.keywordPlus | DIELS-ALDER REACTIONS | - |
dc.subject.keywordPlus | BETA-HYDRIDE ELIMINATION | - |
dc.subject.keywordPlus | ASYMMETRIC CATALYSIS | - |
dc.subject.keywordPlus | ENANTIOSELECTIVE HYDROGENATION | - |
dc.subject.keywordPlus | AEROBIC OXIDATION | - |
dc.subject.keywordPlus | MOLECULAR-OXYGEN | - |
dc.subject.keywordPlus | PALLADIUM(II)-CATALYZED CYCLIZATION | - |
dc.subject.keywordPlus | BIOLOGICAL-PROPERTIES | - |
dc.subject.keywordPlus | VINYLIC SUBSTITUTION | - |
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