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Kinetic and structure-activity studies of the triazolium ion-catalysed benzoin condensation
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dc.contributor.author | Massey, Richard | |
dc.contributor.author | Murray, Jacob | |
dc.contributor.author | Collett, Christopher John | |
dc.contributor.author | Zhu, Jiayun | |
dc.contributor.author | Smith, Andrew D. | |
dc.contributor.author | O'Donoghue, AnnMarie | |
dc.date.accessioned | 2020-12-23T18:30:16Z | |
dc.date.available | 2020-12-23T18:30:16Z | |
dc.date.issued | 2020-12-14 | |
dc.identifier | 271643389 | |
dc.identifier | 756f8a89-853e-4f27-bd50-63560457f78c | |
dc.identifier | 85099772244 | |
dc.identifier | 000609532200011 | |
dc.identifier.citation | Massey , R , Murray , J , Collett , C J , Zhu , J , Smith , A D & O'Donoghue , A 2020 , ' Kinetic and structure-activity studies of the triazolium ion-catalysed benzoin condensation ' , Organic & Biomolecular Chemistry , vol. Advance article . https://doi.org/10.1039/D0OB02207A | en |
dc.identifier.issn | 1477-0520 | |
dc.identifier.other | ORCID: /0000-0002-2104-7313/work/85562421 | |
dc.identifier.uri | https://hdl.handle.net/10023/21201 | |
dc.description.abstract | Steady-state kinetic and structure-activity studies of a series of six triazolium-ion pre-catalysts 2a–2f were investigated for the benzoin condensation under catalytic conditions in a polar solvent environment. Kinetic behaviour was significantly different to that previously reported for a related thiazolium-ion pre-catalyst 1, with the observed levelling of initial rate constants to νmax at high aldehyde concentrations for all triazolium catalysts. Values for νmax for 2a–2f increase with electron withdrawing N-aryl substituents, in agreement with reported optimal synthetic outcomes under catalytic conditions, and vary by 75-fold across the series. The levelling of rate constants supports a change in rate-limiting step and evidence supports the assignment of the Breslow-intermediate forming step to the plateau region. Correlation of νmax reaction data yielded a positive Hammett ρ-value (ρ = +1.66) supporting the build up of electron density adjacent to the triazolium N-Ar in the rate-limiting step favoured by electron withdrawing N-aryl substituents. At lower concentrations of aldehyde, both Breslow-intermediate and benzoin formation are partially rate-limiting. | |
dc.format.extent | 7 | |
dc.format.extent | 1530108 | |
dc.language.iso | eng | |
dc.relation.ispartof | Organic & Biomolecular Chemistry | en |
dc.subject | QD Chemistry | en |
dc.subject | E-NDAS | en |
dc.subject.lcc | QD | en |
dc.title | Kinetic and structure-activity studies of the triazolium ion-catalysed benzoin condensation | en |
dc.type | Journal article | en |
dc.contributor.institution | University of St Andrews. School of Chemistry | en |
dc.identifier.doi | https://doi.org/10.1039/D0OB02207A | |
dc.description.status | Peer reviewed | en |
dc.identifier.url | http://www.rsc.org/suppdata/d0/ob/d0ob02207a/d0ob02207a1.pdf | en |
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