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Insights into NHC-catalyzed oxidative α-C(sp3)−H activation of aliphatic aldehydes and cascade [2 + 3] cycloaddition with azomethine imines

Abstract

To predict whether the catalyst can work efficiently is one of the most challenging questions in the catalysis field. Herein, we suggested that Lewis base organocatalyst can promote the [2 + 3] cyclization by avoiding the poor frontier molecular orbital (FMO) overlap mode involved in the chemical changes for the first time. The density functional theory (DFT) calculations were performed to disclose the detailed mechanism and origin of stereoselectivity of N-heterocyclic carbene (NHC)-catalyzed oxidative α-C(sp3)−H activation of aliphatic aldehydes and cascade [2 + 3] cycloaddition with azomethine imines. The computational results indicate that NHC catalyst can significantly lower the energy barrier of rate- and stereoselectivity-determining [2 + 3] cycloaddition by changing the shoulder-to-head to head-to-head overlap mode to enable the cycloaddition. Therefore, this work would be valuable not only for predicting the efficiency of the organocatalyst in the [2 + n] (n=2, 3, 4) cyclizations, but also for developing the new applications of FMO theory in the organocatalysis field.

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Publication details

The article was received on 16 Mar 2019, accepted on 10 Apr 2019 and first published on 11 Apr 2019


Article type: Paper
DOI: 10.1039/C9CY00526A
Citation: Catal. Sci. Technol., 2019, Accepted Manuscript

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    Insights into NHC-catalyzed oxidative α-C(sp3)−H activation of aliphatic aldehydes and cascade [2 + 3] cycloaddition with azomethine imines

    X. Li, S. Li, Y. Wang, Y. Wang, L. Qu, Z. Li and D. Wei, Catal. Sci. Technol., 2019, Accepted Manuscript , DOI: 10.1039/C9CY00526A

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