Abstract
N-heterocyclic olefins (NHOs) possess an electron-rich and highly polarized C=C double bond due to the donating property of nitrogen atoms. This feature imparts exocyclic carbon atom of NHOs with strong basicity and high nucleophilicity. Although NHOs have been emerging as a new type of organocatalyst and ligand for metal complexes in organic synthesis, chiral NHO-mediated highly enantioselective organic transformations were still elusive. Herein, we developed a new type of chiral amine-derived C2-symmetric NHOs and employed them as efficient chiral bifunctional organocatalysts for asymmetric α-functionalization of β-ketoesters. With as low as 0.1 mol% catalyst loading, the desired amination and trifluoromethylthiolation products were afforded in good yields with high enantioselectivities (up to 99% yield and 99% ee). Experimental studies and theoretical calculation disclosed that hydrogen-bonding interaction upon protonation and other weak interaction between substrate and catalyst were crucial for the enantiocontrol.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (92056107, 22271199, 21801175) and the Sichuan University (2020SCUNL204).
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Supporting information The supporting information is available online at https://chem.scichina.com and https://springerlink.bibliotecabuap.elogim.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.
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Wang, S., Zhang, C., Li, D. et al. New chiral N-heterocyclic olefin bifunctional organocatalysis in α-functionalization of β-ketoesters. Sci. China Chem. 66, 147–154 (2023). https://doi.org/10.1007/s11426-022-1458-4
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DOI: https://doi.org/10.1007/s11426-022-1458-4