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Isothiourea-catalysed enantioselective pyrrolizine synthesis : synthetic and computational studies
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dc.contributor.author | Stark, Daniel Graham | |
dc.contributor.author | Williamson, Patrick | |
dc.contributor.author | Gayner, Emma R | |
dc.contributor.author | Musolino, Stefania Francesca | |
dc.contributor.author | Kerr, Ryan William Frederick | |
dc.contributor.author | Taylor, James Edward | |
dc.contributor.author | Slawin, Alexandra Martha Zoya | |
dc.contributor.author | O'Riordan, Timothy J C | |
dc.contributor.author | Macgregor, Stuart A | |
dc.contributor.author | Smith, Andrew David | |
dc.date.accessioned | 2016-08-19T10:30:14Z | |
dc.date.available | 2016-08-19T10:30:14Z | |
dc.date.issued | 2016-10-14 | |
dc.identifier | 244482624 | |
dc.identifier | df25d7fa-3866-4593-a3f8-5538ca04a20e | |
dc.identifier | 84989257470 | |
dc.identifier | 000385173200010 | |
dc.identifier.citation | Stark , D G , Williamson , P , Gayner , E R , Musolino , S F , Kerr , R W F , Taylor , J E , Slawin , A M Z , O'Riordan , T J C , Macgregor , S A & Smith , A D 2016 , ' Isothiourea-catalysed enantioselective pyrrolizine synthesis : synthetic and computational studies ' , Organic & Biomolecular Chemistry , vol. 14 , no. 38 , pp. 8957-8965 . https://doi.org/10.1039/C6OB01557C | en |
dc.identifier.issn | 1477-0520 | |
dc.identifier.other | ORCID: /0000-0002-2104-7313/work/36567486 | |
dc.identifier.other | ORCID: /0000-0002-9527-6418/work/56861937 | |
dc.identifier.uri | https://hdl.handle.net/10023/9335 | |
dc.description | We thank Syngenta and the EPSRC (grant code EP/K503162/1) (DGS), and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, grant code EP/L016419/1) (ERG,SFM, RWFK) for funding. The European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) ERC Grant Agreement No. 279850 is also acknowledged (JET). ADS thanks the Royal Society for a Wolfson Research Merit Award. | en |
dc.description.abstract | The catalytic enantioselective synthesis of a range of cis-pyrrolizine carboxylate derivatives with outstanding stereocontrol (14 examples,>95:5 dr, >98:2 er) through an isothiourea-catalyzed intramolecular Michael addition-lactonisation and ring opening approach from the corresponding enone acid is reported. An optimised and straightforward three-step synthetic route to the enone acid starting materials from readily available pyrrole-2-carboxaldehydes is delineated, with benzotetramisole (5 mol%) proving the optimal catalyst for the enantioselective process. Ring-opening of the pyrrolizine dihydropyranone products with either MeOH or a range of amines leads to the desired products in excellent yield and enantioselectivity. Computation has been used to probe the factors leading to high stereocontrol, with the formation of the observed cis-steroisomer predicted to be kinetically and thermodynamically favoured. | |
dc.format.extent | 9 | |
dc.format.extent | 3455012 | |
dc.language.iso | eng | |
dc.relation.ispartof | Organic & Biomolecular Chemistry | en |
dc.subject | QD Chemistry | en |
dc.subject | DAS | en |
dc.subject.lcc | QD | en |
dc.title | Isothiourea-catalysed enantioselective pyrrolizine synthesis : synthetic and computational studies | en |
dc.type | Journal article | en |
dc.contributor.sponsor | EPSRC | en |
dc.contributor.sponsor | The Royal Society | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.contributor.institution | University of St Andrews. Biomedical Sciences Research Complex | en |
dc.contributor.institution | University of St Andrews. EaSTCHEM | en |
dc.identifier.doi | https://doi.org/10.1039/C6OB01557C | |
dc.description.status | Peer reviewed | en |
dc.identifier.url | http://www.rsc.org/suppdata/c6/ob/c6ob01557c/c6ob01557c1.zip | en |
dc.identifier.url | http://www.rsc.org/suppdata/c6/ob/c6ob01557c/c6ob01557c2.pdf | en |
dc.identifier.grantnumber | EP/L016419/1 | en |
dc.identifier.grantnumber | WM140071 | en |
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