Work

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

Year: 2009

Type: article

Abstract: 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 alpha,beta-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.

Source: Organic Letters

DOI: 10.1021/ol901545m

Authors: Brooks E. Maki, Eric V. Patterson, Christopher J. Cramer, Karl A. Scheidt

Institutions: Northwestern University, University of Minnesota, Truman State University, Chemistry of Life Processes Institute

Language: English

Topic: N-Heterocyclic Carbenes in Organic and Inorganic Chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: AstraZeneca, National Institute of General Medical Sciences, Division of Chemistry

Awards: G388657058, G682315649