N‑Heterocyclic Carbene Catalyzed Asymmetric Intermolecular Stetter Reaction: Origin of Enantioselectivity and Role of Counterions

The mechanism and the role of KOtBu in an enantioselective NHC-catalyzed Stetter reaction between p-chlorobenzaldehyde and N-acylamido acrylate is established using DFT(M06-2X) methods. The Gibbs free energies are found to be significantly lower for transition states with explicit bound KOtBu as com...

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Published inOrganic letters Vol. 15; no. 19; pp. 5040 - 5043
Main Authors Kuniyil, Rositha, Sunoj, Raghavan B
Format Journal Article
LanguageEnglish
Published United States American Chemical Society 04.10.2013
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Summary:The mechanism and the role of KOtBu in an enantioselective NHC-catalyzed Stetter reaction between p-chlorobenzaldehyde and N-acylamido acrylate is established using DFT(M06-2X) methods. The Gibbs free energies are found to be significantly lower for transition states with explicit bound KOtBu as compared to the conventional pathways without the counterions. An intermolecular proton transfer from HOtBu to the prochiral carbon is identified as the stereocontrolling step. The computed enantioselectivities are in excellent agreement with the experimental results.
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ISSN:1523-7060
1523-7052
DOI:10.1021/ol402375d