Anomalous Z-isomer content in Wittig reaction products from keto-stabilised ylides with ortho-heteroatom substituted benzaldehydes

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dc.contributor.authorByrne, Peter A.
dc.contributor.authorHigham, Lee J.
dc.contributor.authorMcGovern, Pádraic
dc.contributor.authorGilheany, Declan G.
dc.contributor.funderIrish Research Council for Science, Engineering and Technologyen
dc.date.accessioned2019-04-04T14:09:11Z
dc.date.available2019-04-04T14:09:11Z
dc.date.issued2012-10-02
dc.date.updated2019-03-26T18:26:06Z
dc.description.abstractWittig reaction products of keto-stabilised ylides with ortho-substituted benzaldehydes are found to show significantly higher than expected Z-alkene content (up to 50%) compared to analogous reactions of the same ylides with benzaldehyde itself. A cooperative effect is seen whereby the unusual Z-content is further augmented if the ylide bears greater steric bulk in the α′-position. These results are consistent with our previous observations on reactions of all ylide types with aldehydes bearing a β-heteroatom. Significantly, the cooperative effect, previously seen only with semi-stabilised ylides, has now been extended to stabilised ylides. Both the anomalous increase in Z-content and the cooperative effect can be rationalised within the [2+2] cycloaddition mechanism of the Wittig reaction.en
dc.description.sponsorshipIrish Research Council for Science, Engineering and Technology (EMBARK Scholarship)en
dc.description.statusPeer revieweden
dc.description.versionSubmitted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationByrne, P. A., Higham, L. J., McGovern, P. and Gilheany, D. G. (2012) 'Anomalous Z-isomer content in Wittig reaction products from keto-stabilised ylides with ortho-heteroatom substituted benzaldehydes', Tetrahedron Letters, 53(49), pp. 6701-6704. doi: 10.1016/j.tetlet.2012.09.123en
dc.identifier.doi10.1016/j.tetlet.2012.09.123en
dc.identifier.endpage6704en
dc.identifier.issn0040-4039
dc.identifier.journaltitleTetrahedron Lettersen
dc.identifier.startpage6701en
dc.identifier.urihttps://hdl.handle.net/10468/7716
dc.identifier.volume53en
dc.language.isoenen
dc.publisherElsevieren
dc.relation.urihttp://www.sciencedirect.com/science/article/pii/S0040403912017236
dc.rights© 2012 Elsevier Ltd. All rights reserved. This submitted manuscript version is made available under the CC-BY-NC-ND 4.0 licenseen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/en
dc.subjectWittig reaction mechanismen
dc.subjectKeto-stabilised phosphonium ylideen
dc.subjectortho-Substituted benzaldehydesen
dc.subjectKinetic control in Wittig reactionsen
dc.subjectZ-Alkeneen
dc.subject[2+2] Cycloadditionen
dc.titleAnomalous Z-isomer content in Wittig reaction products from keto-stabilised ylides with ortho-heteroatom substituted benzaldehydesen
dc.typeArticle (peer-reviewed)en
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