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Updated: Sep 9, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
DFT Calculation-Assisted Design of Precursors for Nucleophilic 2-Amino Allyl Cations and Their Application in [3 + 2]
Chentong Sun1, Chunhao Yuan2, Zongle Shen1
1School of Pharmaceutical Sciences & Institute of Materia Medica, Medical Science and Technology Innovation Center, Shandong First Medical University & Shandong Academy of Medical Sciences, Jinan 250117, Shandong, P. R. China.
Abstract:
In this work, we developed nucleophilic 2-aminoallyl cations guided by DFT calculations. Computational insights enabled a comprehensive analysis of factors governing N-nucleophilicity and an accurate prediction of cycloaddition reactivity with electron-deficient alkenes. Notably, this study represents the first asymmetric [3 + 2] cycloaddition of amino-allyl cations with exocyclic double bonds, enabling the efficient synthesis of spiro-pyrrolidines with excellent diastereoselectivities and enantioselectivities. Furthermore, the successful gram-scale preparation and derivatization of the products clearly demonstrate the synthetic utility of this methodology.
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