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Article: Concerted Ring Opening and Cycloaddition of Chiral Epoxy Enolsilanes with Dienes.

TitleConcerted Ring Opening and Cycloaddition of Chiral Epoxy Enolsilanes with Dienes.
Authors
Issue Date2015
PublisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www3.interscience.wiley.com/journal/26737/home
Citation
Angewandte Chemie (International Edition), 2015, v. 54 n. 25, p. 7422-7425 How to Cite?
AbstractSilyl-triflate-catalyzed (4+3) cycloadditions of epoxy enolsilanes with dienes provide a mild and chemoselective synthetic route to seven-membered carbocycles. Epoxy enolsilanes containing a terminal enolsilane and a single stereocenter undergo cycloaddition with almost complete conservation of enantiomeric purity, a finding that argues against the involvement of oxyallyl cation intermediates which have been previously proposed for these types of reactions. Reported are theoretical and experimental investigations of the cycloaddition mechanism. The major enantiomers of the cycloadducts are derived from SN2-like reactions of the silylated epoxide with the diene, in which stereospecific ring opening and formation of the two new C-C bonds occur in a single step. Calculations predict, and experiments confirm, that the observed small losses of enantiomeric purity are traced to a triflate-mediated double SN2 cycloaddition pathway.
Persistent Identifierhttp://hdl.handle.net/10722/211626
ISSN
2015 Impact Factor: 11.709
2015 SCImago Journal Rankings: 6.229

 

DC FieldValueLanguage
dc.contributor.authorKrenske, EH-
dc.contributor.authorLam, SYY-
dc.contributor.authorNg, JPL-
dc.contributor.authorLo, B-
dc.contributor.authorLam, SK-
dc.contributor.authorChiu, P-
dc.contributor.authorHouk, KN-
dc.date.accessioned2015-07-21T02:05:41Z-
dc.date.available2015-07-21T02:05:41Z-
dc.date.issued2015-
dc.identifier.citationAngewandte Chemie (International Edition), 2015, v. 54 n. 25, p. 7422-7425-
dc.identifier.issn1433-7851-
dc.identifier.urihttp://hdl.handle.net/10722/211626-
dc.description.abstractSilyl-triflate-catalyzed (4+3) cycloadditions of epoxy enolsilanes with dienes provide a mild and chemoselective synthetic route to seven-membered carbocycles. Epoxy enolsilanes containing a terminal enolsilane and a single stereocenter undergo cycloaddition with almost complete conservation of enantiomeric purity, a finding that argues against the involvement of oxyallyl cation intermediates which have been previously proposed for these types of reactions. Reported are theoretical and experimental investigations of the cycloaddition mechanism. The major enantiomers of the cycloadducts are derived from SN2-like reactions of the silylated epoxide with the diene, in which stereospecific ring opening and formation of the two new C-C bonds occur in a single step. Calculations predict, and experiments confirm, that the observed small losses of enantiomeric purity are traced to a triflate-mediated double SN2 cycloaddition pathway.-
dc.languageeng-
dc.publisherWiley - V C H Verlag GmbH & Co. KGaA. The Journal's web site is located at http://www3.interscience.wiley.com/journal/26737/home-
dc.relation.ispartofAngewandte Chemie (International Edition)-
dc.titleConcerted Ring Opening and Cycloaddition of Chiral Epoxy Enolsilanes with Dienes.-
dc.typeArticle-
dc.identifier.emailChiu, P: pchiu@hku.hk-
dc.identifier.authorityChiu, P=rp00680-
dc.identifier.doi10.1002/anie.201503003-
dc.identifier.pmid25951012-
dc.identifier.hkuros244259-
dc.identifier.volume54-
dc.identifier.issue25-
dc.identifier.spage7422-
dc.identifier.epage7425-
dc.publisher.placeGermany-

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