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dc.contributor.authorFuentes García, José Antonio
dc.contributor.authorDurrani, Jamie
dc.contributor.authorLeckie, Stuart M.
dc.contributor.authorCrawford, Luke
dc.contributor.authorBuehl, Michael
dc.contributor.authorClarke, Matt
dc.identifier.citationFuentes García , J A , Durrani , J , Leckie , S M , Crawford , L , Buehl , M & Clarke , M 2016 , ' Isomerisation versus carbonylative pathways in the hydroxy-carbonylation, methoxy-carbonylation, and amino-carbonylation of N -tosyl-3-pyrroline ' , Catalysis Science & Technology , vol. 6 , no. 20 , pp. 7477-7485 .
dc.identifier.otherPURE: 245325973
dc.identifier.otherPURE UUID: c2724c9b-2e3a-4b1f-bbb9-4a50b5f3a51b
dc.identifier.otherBibtex: urn:8e868a357cc1204586f29c6cc2a2e851
dc.identifier.otherScopus: 84991042527
dc.identifier.otherORCID: /0000-0002-1095-7143/work/48131841
dc.identifier.otherORCID: /0000-0002-2444-1244/work/59464631
dc.identifier.otherWOS: 000386210100012
dc.descriptionThe authors thank the EPSRC for funding, primarily from grant number EP/M003868/1.en
dc.description.abstractThe reactivity of N-tosyl-3-pyrroline is significantly lower than that of mono-substituted alkenes in Pd catalysed methoxycarbonylation reactions. For example, most bulky diphosphine/ Pd catalysts, including the well-known Pd catalyst derived from 1,2-bis(di-tert-butylphosphino)xylene (DTBPX), were found to give no product at all in the methoxycarbonylation of N-tosyl-3-pyrroline. The competing pathways in methoxycarbonylation of N-methane-sulfonyl-3-pyrroline using Pd/ DTBPX were studied using DFT calculations; these show that the coordination of the alkene is unfavourable, and once coordinated, isomerisation is a lower energy pathway that ultimately leads to an alternative product. Experimentally a side product resulting from alkene isomerisation and addition of methanol is formed slowly (if CO is present), and rapidly if CO is not. A less bulky derivative of DTBPX forms the required alkene complex with much lower barriers. A study has been made of the enantioselective carbonylation of N-tosyl-3-pyrroline using water, methanol or aniline as nucleophile. This study revealed that there is a range of possible products with most of these initiated by a Pd-catalysed isomerisation of the alkene. Using less bulky members of the Pd/Phanephos family of catalysts, it is possible to produce the methoxycarbonylation product from this poorly reactive alkene with reasonably good chemoselectivity and around 80% e.e. at higher pressures of CO.
dc.relation.ispartofCatalysis Science & Technologyen
dc.rightsCopyright 2016 the Authors. This work is made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at
dc.subjectQD Chemistryen
dc.titleIsomerisation versus carbonylative pathways in the hydroxy-carbonylation, methoxy-carbonylation, and amino-carbonylation of N-tosyl-3-pyrrolineen
dc.typeJournal articleen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.description.statusPeer revieweden

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