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The Impact of Solvent Polarity on N-Heterocyclic Carbene-Catalyzed β-Protonations of Homoenolate Equivalents

Maki, B. E.; Patterson, E. V.; Cramer, C. J.; Scheidt, K. A.
Org. Lett. 2009, 11, 3942.

N-Heterocyclic carbenes have been demonstrated to react through divergent pathways under the same conditions. Experimental and computational evidence demonstrates that the ability to favor generation of homoenolate equivalents from α,β-unsaturated aldehydes versus the oxidation of aldehydes to esters is highly dependent upon the choice of solvent. The solvation environment plays an important role due to the mechanistic differences in these processes, with polar protic solvent favoring the oxidation process due to solvation of intermediates with greater charge separation.