Morita–Baylis–Hillman Reaction: ESI-MS(/MS) Investigation with Charge Tags and Ionic Liquid Effect Origin Revealed by DFT Calculations

The use of a charge-tagged acrylate derivative bearing an imidazolium tag to study the Morita–Baylis–Hillman reaction via ESI-MS(/MS) monitoring and the effect of such tag (imidazolium cations and ion pairs) over TSs is described. The ionic nature of the substrate was meant to facilitate ESI transfe...

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Bibliographic Details
Published in:Journal of organic chemistry 2014-06, Vol.79 (11), p.5239-5248
Main Authors: Rodrigues, Thyago S, Silva, Valter H. C, Lalli, Priscila M, de Oliveira, Heibbe C. B, da Silva, Wender A, Coelho, Fernando, Eberlin, Marcos N, Neto, Brenno A. D
Format: Article
Language:English
Subjects:
Acetonitriles - chemistry
Acrylates
Catalysis
Imidazoles - chemistry
Indicators and Reagents - chemistry
Ionic Liquids - chemistry
Protons
Solvents - chemistry
Spectrometry, Mass, Electrospray Ionization
Tandem Mass Spectrometry
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Summary:The use of a charge-tagged acrylate derivative bearing an imidazolium tag to study the Morita–Baylis–Hillman reaction via ESI-MS(/MS) monitoring and the effect of such tag (imidazolium cations and ion pairs) over TSs is described. The ionic nature of the substrate was meant to facilitate ESI transfer to the gas phase for direct mass spectrometric analysis. The detection and characterization of charged intermediates has suggested major reaction pathways. DFT calculations considering the effect of a polar and protic solvent (methanol), of a polar and aprotic solvent (acetonitrile), and of no solvent (gas phase) were used to predict possible TSs through a common accepted intermediate. The controversial proton transfer step, which may proceed via Aggarwal’s or McQuade’s proposals, was evaluated. Calculations predicted the formation of electrostatic intermediate complexes with both the cation and anion when charge-tagged reagents are used. These complexes contribute to the positive ionic liquid effect, and based on the formation of these unique complexes, a rationale for the ionic liquid effect is proposed. These complexes also pointed to a plausible explanation for the positive ionic liquid effect observed in several reactions that are difficult to be carried out in organic solvents but have shown a beneficial effect when performed in ionic liquids.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo500799j