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Isomerisation versus carbonylative pathways in the hydroxy-carbonylation, methoxy-carbonylation, and amino-carbonylation of N-tosyl-3-pyrroline
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dc.contributor.author | Fuentes García, José Antonio | |
dc.contributor.author | Durrani, Jamie | |
dc.contributor.author | Leckie, Stuart M. | |
dc.contributor.author | Crawford, Luke | |
dc.contributor.author | Buehl, Michael | |
dc.contributor.author | Clarke, Matt | |
dc.date.accessioned | 2017-08-22T23:32:26Z | |
dc.date.available | 2017-08-22T23:32:26Z | |
dc.date.issued | 2016-10-21 | |
dc.identifier | 245325973 | |
dc.identifier | c2724c9b-2e3a-4b1f-bbb9-4a50b5f3a51b | |
dc.identifier | 84991042527 | |
dc.identifier | 000386210100012 | |
dc.identifier.citation | Fuentes 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 . https://doi.org/10.1039/C6CY01268J | en |
dc.identifier.issn | 2044-4753 | |
dc.identifier.other | Bibtex: urn:8e868a357cc1204586f29c6cc2a2e851 | |
dc.identifier.other | ORCID: /0000-0002-1095-7143/work/48131841 | |
dc.identifier.other | ORCID: /0000-0002-2444-1244/work/59464631 | |
dc.identifier.uri | https://hdl.handle.net/10023/11527 | |
dc.description | The authors thank the EPSRC for funding, primarily from grant number EP/M003868/1. | en |
dc.description.abstract | The 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.format.extent | 9 | |
dc.format.extent | 1926506 | |
dc.language.iso | eng | |
dc.relation.ispartof | Catalysis Science & Technology | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Isomerisation versus carbonylative pathways in the hydroxy-carbonylation, methoxy-carbonylation, and amino-carbonylation of N-tosyl-3-pyrroline | en |
dc.type | Journal article | en |
dc.contributor.sponsor | EPSRC | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | https://doi.org/10.1039/C6CY01268J | |
dc.description.status | Peer reviewed | en |
dc.date.embargoedUntil | 2017-08-22 | |
dc.identifier.url | http://www.rsc.org/suppdata/c6/cy/c6cy01268j/c6cy01268j1.pdf | en |
dc.identifier.grantnumber | EP/M003868/1 | en |
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