Kuniyil, Rositha ; Sunoj, Raghavan B. (2013) N-heterocyclic carbene catalyzed asymmetric intermolecular stetter reaction: origin of enantioselectivity and role of counterions Organic Letters, 15 (19). pp. 5040-5043. ISSN 1523-7060
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Official URL: http://pubs.acs.org/doi/abs/10.1021/ol402375d
Related URL: http://dx.doi.org/10.1021/ol402375d
Abstract
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.
| Item Type: | Article |
|---|---|
| Source: | Copyright of this article belongs to American Chemical Society. |
| ID Code: | 109753 |
| Deposited On: | 02 Aug 2017 11:48 |
| Last Modified: | 02 Aug 2017 11:48 |
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