Mechanistic features of the copper-free Sonogashira reaction from ESI-MS

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dc.contributor.authorAhmadi, Zohrab
dc.contributor.authorYunker, Lars P. E.
dc.contributor.authorOliver, Allen G.
dc.contributor.authorMcIndoe, J. Scott
dc.date.accessioned2017-04-24T20:59:51Z
dc.date.available2017-04-24T20:59:51Z
dc.date.copyright2015en_US
dc.date.issued2015
dc.description.abstractThe mechanism of the Sonogashira reaction in methanol was studied in detail using pressurized sample infusion electrospray ionization mass spectrometry (PSI-ESI-MS). Several key intermediates were identified and their structures were assigned by MS/MS studies. Cationic and anionic charged-tagged substrates were employed to look into the mechanism of this reaction from variety of angles. A reverse kinetic isotope effect was observed in which the reaction rate is accelerated in deuterated solvents (kH/kD = 0.6). The reaction was found to be zero order with respect to the aryl iodide and first order with respect to the phenylacetylene. A Hammett parameter of ρ = 1.4 indicates that the reaction is more favorable for aryl iodides with para EWGs. No evidence of product inhibition, dimerization of palladium catalyst, or agglomeration were observed. However, catalyst decomposition was inferred from a non-zero intercept in the plot of catalyst loading versus reaction rate. Monitoring the reaction by PSI-ESI-(-)MS on neutral and negatively charged substrates at variety of concentrations and conditions did not reveal any detectable anionic palladium complexes. Likewise no evidence of carbopalladation and relevant intermediates in the absence of a base was observed.en_US
dc.description.reviewstatusRevieweden_US
dc.description.scholarlevelFacultyen_US
dc.description.sponsorshipNSERCen_US
dc.identifier.citationAhmadi, Z., Yunker, L., Oliver, A., & McIndoe, J. (2015). Mechanistic features of the copper-free sonogashira reaction from ESI-MS. Dalton Transactions, 44(47), 20367-20375.en_US
dc.identifier.urihttps://dx.doi.org/10.1039/C5DT02889B
dc.identifier.urihttp://hdl.handle.net/1828/7978
dc.language.isoenen_US
dc.publisherDalton Transactionsen_US
dc.subjectcatalysis
dc.subjectmass spectrometry
dc.subjectelectrospray ionization
dc.subjectreal-time monitoring
dc.subjectSonogashira coupling
dc.subjectHeck alkynylation
dc.subject.departmentDepartment of Chemistry
dc.titleMechanistic features of the copper-free Sonogashira reaction from ESI-MSen_US
dc.typePostprinten_US

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