The modern interpretation of the Wittig reaction mechanism

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dc.contributor.author Byrne, Peter A.
dc.contributor.author Gilheany, Declan G.
dc.date.accessioned 2019-04-04T11:55:47Z
dc.date.available 2019-04-04T11:55:47Z
dc.date.issued 2013-05-14
dc.identifier.citation Byrne, P. A. and Gilheany, D. G. (2013) 'The modern interpretation of the Wittig reaction mechanism', Chemical Society Reviews, 42(16), pp. 6670-6696. doi: 10.1039/C3CS60105F en
dc.identifier.volume 42 en
dc.identifier.startpage 6670 en
dc.identifier.endpage 6696 en
dc.identifier.issn 0306-0012
dc.identifier.uri http://hdl.handle.net/10468/7712
dc.identifier.doi 10.1039/C3CS60105F en
dc.description.abstract The mechanism of the Wittig reaction has long been a contentious issue in organic chemistry. Even now, more than 50 years after its announcement, its presentation in many modern undergraduate textbooks is either overly simplified or entirely inaccurate. In this review, we gather together the huge body of evidence that has been amassed to show that the Li salt-free Wittig reactions of non-stabilised, semi-stabilised and stabilised ylides all occur under kinetic control by a common mechanism in which oxaphosphetane (OPA) is the first-formed and only intermediate. The numerous recent significant additions to the subject – including computational studies and experimental material pertinent to both steps of the reaction (OPA formation and its decomposition) are discussed in detail, and the currently accepted explanations for the source of the stereoselectivity in Wittig reactions are given. We also present the other mechanistic proposals that have been made during the history of the Wittig reaction, and show how they are unable to account for all of the experimental evidence that is now available. Details of certain experimental facts to do with Wittig reactions in the presence of Li cation are also included, although the precise mechanistic details of such reactions are yet to be established conclusively. We make the case that a clear distinction should henceforth be made between the unknown “Li-present” and the now well-established “Li salt-free” Wittig mechanisms. en
dc.description.sponsorship Irish Research Council for Science, Engineering and Technology (IRCSET EMBARK Scholarship) en
dc.format.mimetype application/pdf en
dc.language.iso en en
dc.publisher Royal Society of Chemistry (RSC) en
dc.relation.uri https://pubs.rsc.org/en/content/articlelanding/2013/cs/c3cs60105f
dc.rights © The Royal Society of Chemistry 2013 en
dc.subject Alkene en
dc.subject Betaine en
dc.subject Organophosphorus compound en
dc.subject Wittig reaction en
dc.title The modern interpretation of the Wittig reaction mechanism en
dc.type Article (peer-reviewed) en
dc.internal.authorcontactother Peter Byrne, Chemistry, University College Cork, Cork, Ireland. +353-21-490-3000 Email: peter.byrne@ucc.ie en
dc.internal.availability Full text available en
dc.date.updated 2019-03-26T17:57:29Z
dc.description.version Submitted Version en
dc.internal.rssid 383418262
dc.contributor.funder Irish Research Council for Science, Engineering and Technology en
dc.description.status Peer reviewed en
dc.identifier.journaltitle Chemical Society Reviews en
dc.internal.copyrightchecked No
dc.internal.licenseacceptance Yes en
dc.internal.IRISemailaddress peter.byrne@ucc.ie en
dc.identifier.eissn 1460-4744


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