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C-H alkylation of pyridines with olefins catalyzed by imidazolin-2-iminato-ligated rare-earth alkyl complexes

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Abstract

An array of rare-earth bis(aminobenzyl) complexes supported by imidazolin-2-iminato ligands were synthesized and structurally characterized. These complexes showed high activity towards ortho-Csp2–H alkylation of 2-alkylpyridines and benzylic Csp3–H alkylation of 2,6-dialkylpyridines with alkenes. A wide range of alkyl or aryl substituted olefin substrates are compatible, providing an atom-economical route to linear or branched alkylated pyridine derivatives in moderate to high yields (45 examples, up to 99% yield). The primary study suggested that the asymmetric version of Csp3–H alkylation of 2,4,6-collidine with allylbenzene was feasible with chiral imidazolin-2-iminato-ligated scandium(III) complexes, and good yield with moderate enantioselectivity was obtained (84% yield, 84:16 er). Mechanistic investigations including kinetic isotope effect (KIE) experiments and density functional theory (DFT) calculations shed light on the catalytic cycle and the origin of enantiocontrol.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2022YFA1504301), the National Natural Science Foundation of China (92056107, 22271199, 92256303, 21890723), and Sichuan University (2020SCUNL204).

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Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu, 610064, China

    Dawei Li, Lichao Ning, Qiliang Luo, Shiyu Wang, Xiaoming Feng & Shunxi Dong

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  1. Dawei Li
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  2. Lichao Ning
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  3. Qiliang Luo
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  4. Shiyu Wang
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  5. Xiaoming Feng
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Correspondence to Shunxi Dong.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.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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Li, D., Ning, L., Luo, Q. et al. C-H alkylation of pyridines with olefins catalyzed by imidazolin-2-iminato-ligated rare-earth alkyl complexes. Sci. China Chem. 66, 1804–1813 (2023). https://doi.org/10.1007/s11426-023-1588-8

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