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The mechanism studies of catalytic chemoselective conjugate addition of amino alcohols to α,β-unsaturated ester

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Abstract

The competing mechanisms of silver-/aminolithium-catalyzed hydrofunctionalization of α,β-unsaturated ester with an amino alcohol have been systematically studied with the DFT methods. Here, the acidity of a weaker nucleophile OH group of an amino alcohol is significantly higher than that of NH2 group, so it is easy to deprotonate by Ag(HMDS)/dppe. However, the generated Ag–O bond is more stable than the corresponding Ag–N bond. Therefore, the OH group shows higher reactivity than the NH2 group in the presence of a Lewis acid/Brønsted base pair catalyst. Then, α,β-unsaturated esters can be inserted into corresponding Ag–O bonds to obtain alkyl silver species. Alkyl silver can be protonated by bis(trimethylsilyl)amines to obtain hydrogen functionalized products and regenerate silver amino active compounds Ag(HMDS)/dppe.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 21703195 and 31601447), the Third Outstanding Young Talent Project of Xuchang University, the Fifth Outstanding Young Teacher Project of Xuchang University, and Training Plan of Young Core Teachers in Universities of Henan Province for the year of 2019 (No. 2019GGJS211).

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Authors and Affiliations

  1. College of Chemical and Materials Engineering, Xuchang University of China, No.88 of Bayi Road, Henan Province, Xuchang, 461000, People’s Republic of China

    Peilin Han, Xiaowei Zhang, Xiaoxiao Hou, Hui Wang & Chunhui Liu

  2. School of Chemistry and Chemical Engineering, Henan Institute of Science and Technology, Henan Province, Xinxiang, 453003, People’s Republic of China

    Huijuan Han

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  1. Peilin Han
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Han, P., Han, H., Zhang, X. et al. The mechanism studies of catalytic chemoselective conjugate addition of amino alcohols to α,β-unsaturated ester. Theor Chem Acc 140, 6 (2021). https://doi.org/10.1007/s00214-020-02711-y

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