The mechanism of phosphonium ylide alcoholysis and hydrolysis: concerted addition of the O-H bond across the P=C bond

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dc.contributor.authorByrne, Peter A.
dc.contributor.authorGilheany, Declan G.
dc.contributor.funderScience Foundation Irelanden
dc.date.accessioned2019-04-04T11:03:56Z
dc.date.available2019-04-04T11:03:56Z
dc.date.issued2016-06-06
dc.date.updated2019-03-26T17:41:56Z
dc.description.abstractThe previous work on the hydrolysis and alcoholysis reactions of phosphonium ylides is summarized and reviewed in the context of their currently accepted mechanisms. Several experimental facts relating to ylide hydrolysis and to salt and ylide alcoholysis are shown to conflict with those mechanisms. In particular, we demonstrate that the pK(a) values of water and alcohols are too high in organic media to bring about protonation of ylide. Therefore, we propose concerted addition of the water or alcohol O-H bond across the ylide P=C bond. In support of this, we provide NMR spectroscopic evidence for equilibrium between ylide and aclohol that does not require the involvement of phosphonium hydroxide. We report the first P-alkoxyphosphorane to be characterised by NMR spectroscopy that does not undergo exchange on an NMR timescale. Two-dimensional NMR spectroscopic techniques have been applied to the characterisation to P-alkoxyphosphoranes for the first time.en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationByrne, P. A. and Gilheany, D. G. (2016) 'The Mechanism of Phosphonium Ylide Alcoholysis and Hydrolysis: Concerted Addition of the O−H Bond Across the P=C Bond', Chemistry – A European Journal, 22(27), pp. 9140-9154. doi: 10.1002/chem.201600530en
dc.identifier.doi10.1002/chem.201600530en
dc.identifier.eissn1521-3765
dc.identifier.endpage9154en
dc.identifier.issn0947-6539
dc.identifier.journaltitleChemistry - A European Journalen
dc.identifier.startpage9140en
dc.identifier.urihttps://hdl.handle.net/10468/7706
dc.identifier.volume22en
dc.language.isoenen
dc.publisherWileyen
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI Research Centres/12/RC/2275/IE/Synthesis and Solid State Pharmaceutical Centre (SSPC)/en
dc.relation.urihttps://onlinelibrary.wiley.com/doi/full/10.1002/chem.201600530
dc.rights© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the peer reviewed version of the following article: P. A. Byrne, D. G. Gilheany, Chem. Eur. J. 2016, 22, 9140., which has been published in final form at https://doi.org/10.1002/chem.201600530 This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.en
dc.subjectCatalytic Wittig reactionen
dc.subjectNuclear-magnetic-resonanceen
dc.subjectNuclear magnetic resonanceen
dc.subjectTertiary phosphine oxidesen
dc.subjectAlkaline hydrolysisen
dc.subjectThermal decompositionen
dc.subjectEquilibrium aciditiesen
dc.subjectHeteroarylphosphorus compoundsen
dc.subjectNucleophilic displacementen
dc.subjectAlkoxyphosphonium halidesen
dc.subjectSubstitution reactionsen
dc.subjectAlkoxyphosphoraneen
dc.subjectConcerted additionsen
dc.subjectHypervalent compoundsen
dc.subjectReaction intermediatesen
dc.subjectYlidesen
dc.titleThe mechanism of phosphonium ylide alcoholysis and hydrolysis: concerted addition of the O-H bond across the P=C bonden
dc.typeArticle (peer-reviewed)en
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