Show simple item record

Files in this item

Thumbnail

Item metadata

dc.contributor.authorHalford-McGuff, John
dc.contributor.authorSlawin, Alexandra M. Z.
dc.contributor.authorWatson, Allan J. B.
dc.date.accessioned2023-02-24T11:30:18Z
dc.date.available2023-02-24T11:30:18Z
dc.date.issued2023-03-17
dc.identifier283394757
dc.identifier54acb7c1-538e-40dc-8d2a-33e91af1b8e5
dc.identifier85149033773
dc.identifier.citationHalford-McGuff , J , Slawin , A M Z & Watson , A J B 2023 , ' Steric parameterization delivers a reciprocally predictive model for substrate reactivity and catalyst turnover in Rh-catalyzed diyne-alkyne [2+2+2] cycloadditions ' , ACS Catalysis , vol. 13 , no. 6 , pp. 3463–3470 . https://doi.org/10.1021/acscatal.2c06300en
dc.identifier.issn2155-5435
dc.identifier.otherORCID: /0000-0002-9527-6418/work/129708829
dc.identifier.otherORCID: /0000-0002-1582-4286/work/129709731
dc.identifier.urihttps://hdl.handle.net/10023/27053
dc.descriptionFunding: J.M.H.-M. thanks the EaSI-CAT CDT and the University of St Andrews for a PhD studentship. A.J.B.W. thanks the Leverhulme Trust for a Research Fellowship.en
dc.description.abstractThe Rh-catalyzed [2 + 2 + 2] cycloaddition of diynes and alkynes is a synthetically useful transformation that rapidly constructs complex scaffolds and has been used extensively for >70 years. Despite this utility, substrate reactivity issues persist, which are not mechanistically defined. Here, we provide a general predictive model for reactivity and turnover for this reaction. Contrary to the proposed electronic model, this is a predominately sterically driven process where productive turnover is proportional to alkyne steric parameters. This model allows for a priori prediction of catalyst loading, turnover, and reaction yield based on a simple assessment of the steric parameter (e.g., A-value) of the alkyne. The relationship is reciprocal, allowing A-values to be calculated from observed turnover.
dc.format.extent8
dc.format.extent2741530
dc.language.isoeng
dc.relation.ispartofACS Catalysisen
dc.subjectCatalysisen
dc.subjectCycloadditionen
dc.subjectMechanismen
dc.subjectParameterizationen
dc.subjectRhodiumen
dc.subjectQD Chemistryen
dc.subjectDASen
dc.subjectMCCen
dc.subject.lccQDen
dc.titleSteric parameterization delivers a reciprocally predictive model for substrate reactivity and catalyst turnover in Rh-catalyzed diyne-alkyne [2+2+2] cycloadditionsen
dc.typeJournal articleen
dc.contributor.sponsorIBioICen
dc.contributor.sponsorThe Leverhulme Trusten
dc.contributor.institutionUniversity of St Andrews. School of Chemistryen
dc.contributor.institutionUniversity of St Andrews. EaSTCHEMen
dc.contributor.institutionUniversity of St Andrews. Sir James Mackenzie Institute for Early Diagnosisen
dc.identifier.doi10.1021/acscatal.2c06300
dc.description.statusPeer revieweden
dc.identifier.grantnumberen
dc.identifier.grantnumberRF-2022-014en


This item appears in the following Collection(s)

Show simple item record