A multi-pronged mechanistic study of the phosphine-mediated conjugate addition of an alcohol to an acetylenic ester

The conjugate addition of an alcohol to a butynoate ester using an organophosphine catalyst was monitored using pressurized sample infusion electrospray ionization mass spectrometry (PSI-ESI-MS), together with 31 P and 1 H NMR spectroscopy. The combination of methods allowed examination of the react...

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Bibliographic Details
Published in:New journal of chemistry 2014-01, Vol.38 (11), p.5382-5390
Main Authors: Stoddard, Rhonda L., Luo, Jingwei, van der Wal, Nicole, O'Rourke, Natasha F., Wulff, Jeremy E., McIndoe, J. Scott
Format: Article
Language:English
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Summary:The conjugate addition of an alcohol to a butynoate ester using an organophosphine catalyst was monitored using pressurized sample infusion electrospray ionization mass spectrometry (PSI-ESI-MS), together with 31 P and 1 H NMR spectroscopy. The combination of methods allowed examination of the reaction progress from the perspective of reactants and products ( 1 H NMR) and insights into behaviors of the reaction intermediates and formation of byproducts ( 31 P NMR and MS). The resulting traces could be closely approximated through numerical modeling by appropriate selection of rate constants, and a sound understanding of the mechanism and the means by which oligomeric byproducts are formed allows a rational approach to experimental design.
ISSN:1144-0546
1369-9261
DOI:10.1039/C4NJ01070A