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dc.contributor.authorFuentes García, José Antonio
dc.contributor.authorPhillips, Scott David
dc.contributor.authorClarke, Matt
dc.date.accessioned2013-02-11T16:31:04Z
dc.date.available2013-02-11T16:31:04Z
dc.date.issued2012-12-10
dc.identifier.citationFuentes García , J A , Phillips , S D & Clarke , M 2012 , ' New phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketones ' , Chemistry Central Journal , vol. 6 , 151 . https://doi.org/10.1186/1752-153X-6-151en
dc.identifier.issn1752-153X
dc.identifier.otherPURE: 45306853
dc.identifier.otherPURE UUID: 826103ba-5110-4ad6-9b4b-fb178463eaec
dc.identifier.otherWOS: 000313133100001
dc.identifier.otherScopus: 84872177314
dc.identifier.otherORCID: /0000-0002-2444-1244/work/59464594
dc.identifier.urihttp://hdl.handle.net/10023/3353
dc.description.abstractEnantioselective hydrogenation of ketones is a key reaction in organic chemistry. In the past, we have attempted to deal with some unsolved challenges in this arena by introducing chiral tridentate phosphine-diamine/Ru catalysts. New catalysts and new applications are presented here, including the synthesis of phosphine-amino-alcohol P,N,OH ligands derived from (R,S)-1-amino-2-indanol, (S,S)-1-amino-2-indanol and a new chiral P,N,N ligand derived from (R,R)-1,2-diphenylethylenediamine. Ruthenium pre-catalysts of type [RuCl2(L)(DMSO)] were isolated and then examined in the hydrogenation of ketones. While the new P,N,OH ligand based catalysts are poor, the new P,N,N system gives up to 98% e.e. on substrates that do not react at all with most catalysts. A preliminary attempt at realising a new delta lactone synthesis by organocatalytic Michael addition between acetophenone and acrylonitrile, followed by asymmetric hydrogenation of the nitrile functionalised ketone is challenging in part due to the Michael addition chemistry, but also since Noyori pressure hydrogenation catalysts gave massively reduced reactivity relative to their performance for other acetophenone derivatives. The Ru phosphine-diamine system allowed quantitative conversion and around 50% e.e. The product can be converted into a delta lactone by treatment with KOH with complete retention of enantiomeric excess. This approach potentially offers access to this class of chiral molecules in three steps from the extremely cheap building blocks acrylonitrile and methyl-ketones; we encourage researchers to improve on our efforts in this potentially useful but currently flawed process.
dc.format.extent6
dc.language.isoeng
dc.relation.ispartofChemistry Central Journalen
dc.rights© 2012 Fuentes et al.; licensee Chemistry Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.en
dc.subjectP,N,N ligandsen
dc.subjectEstersen
dc.subjectAsymmetric synthesisen
dc.subjectHydroformylationen
dc.subjectChiral alcoholsen
dc.subjectH-2 Hydrogenationen
dc.subjectIminesen
dc.subjectOrganocatalysisen
dc.subjectHydrogenationen
dc.subjectEfficienten
dc.subjectAcrylonitrileen
dc.subjectP,N,O ligandsen
dc.subjectHomogeneous catalysisen
dc.subjectKeto-nitrilesen
dc.subjectMichael additionen
dc.subjectAldehydesen
dc.subjectComplexesen
dc.subjectQD Chemistryen
dc.subject.lccQDen
dc.titleNew phosphine-diamine and phosphine-amino-alcohol tridentate ligands for ruthenium catalysed enantioselective hydrogenation of ketones and a concise lactone synthesis enabled by asymmetric reduction of cyano-ketonesen
dc.typeJournal articleen
dc.description.versionPublisher PDFen
dc.contributor.institutionUniversity of St Andrews.School of Chemistryen
dc.contributor.institutionUniversity of St Andrews.EaSTCHEMen
dc.identifier.doihttps://doi.org/10.1186/1752-153X-6-151
dc.description.statusPeer revieweden


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