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dc.contributor.authorCzauderna, Christine
dc.contributor.authorJarvis, Amanda
dc.contributor.authorHeutz, Frank
dc.contributor.authorCordes, David Bradford
dc.contributor.authorSlawin, Alexandra Martha Zoya
dc.contributor.authorvan der Vlugt, Jarl Ivar
dc.contributor.authorKamer, Paul C J
dc.identifier.citationCzauderna , C , Jarvis , A , Heutz , F , Cordes , D B , Slawin , A M Z , van der Vlugt , J I & Kamer , P C J 2015 , ' Chiral wide bite angle diphosphine ligands : synthesis, coordination chemistry and application in Pd-catalyzed allylic alkylation ' , Organometallics , vol. 34 , no. 9 , pp. 1608-1618 .
dc.identifier.otherPURE: 181751317
dc.identifier.otherPURE UUID: 87b28f90-5d29-4967-916f-0aaeff0241a0
dc.identifier.otherScopus: 84929168068
dc.identifier.otherORCID: /0000-0002-5366-9168/work/28024003
dc.identifier.otherORCID: /0000-0002-9527-6418/work/56861432
dc.identifier.otherWOS: 000354504200003
dc.descriptionThis work was supported by an EASTCHEM fellowship (to C.F.C.) and by the European Union, through a Marie Curie Excellence Grant MEXT-2004-014320. A.G.J. thanks the UK Catalysis Hub for resources and support provided via our membership of the UK Catalysis Hub Consortium and funded by EPSRC (portfolio grants EP/K014706/1, EP/K014668/1, EP/K014854/1 and EP/K014714/1) and the EPSRC for EPSRC Critical mass grant ‘Clean catalysis for sustainable development’ (EP/J018139/1). J.I.v.d.V. thanks the ERC for a Starting Grant 2790097. F.J.L.H. thanks the European Union (Marie Curie ITN SusPhos, Grant Agreement No. 317404) for financial support.en
dc.description.abstractA series of diphosphine ligands bearing ester- and ether-modified diphenylether backbones have been prepared. The introduction of carboxylic acid or ether auxiliaries in the ortho-positions relative to the diphenylphosphine groups was achieved via straightforward four-step synthetic protocols, prior to introduction of the phosphines. The electronic properties of these backbone-modified DPEPhos ligands were evaluated by probing the relevant carbonyl stretching frequencies (νCO) of Ni(CO)2(PP) species (PP = diphosphine) using IR spectroscopy and by determining the phosphorus-selenium coupling constant JSe-P of phosphine selenide derivatives using 31P{1H} NMR spectroscopy. Also the X-ray structure for the bis(carbonyl)nickel(0) species with one of the ligands is reported. The [Pd(η3-allyl)(PP)]-complexes were characterized by multinuclear NMR spectroscopy and applied in the asymmetric allylic alkylation of l,3-diphenyl-2-propenyl acetate and cyclohex-2-enyl acetate with dimethyl malonate in order to benchmark their catalytic potential. The enantioselectivity (ranging from 3 to 70 %) was found to depend on the size of the chiral auxiliary introduced within the diphenyl ether backbone and its proximity to the phosphorus donor groups and hence to the active metal centre. These studies revealed that substituents on the backbone have only a minor effect on the electronic character of the diphenylphosphine groups.
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Organometallics, copyright © 2015 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see:
dc.subjectQD Chemistryen
dc.titleChiral wide bite angle diphosphine ligands : synthesis, coordination chemistry and application in Pd-catalyzed allylic alkylationen
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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