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Updated: Sep 2, 2025

Preparation of Enantiopure Non-Activated Aziridines and Synthesis of Biemamide B, D, and epiallo-Isomuscarine
Published on: June 13, 2022
Mechanism of the Fe(iii)-catalyzed synthesis of hexahydropyrimidine with α-phenylstyrene: a DFT study
Yaxuan Cheng1, Siwei Yang1, Chaoyu Zhao1
1Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, College of Chemistry, Jilin University Liutiao Road 2 Changchun 130023 China huiling@jlu.edu.cn.
Abstract:
It is very important to develop multiple C-H substitution reactions of simple alkenes to obtain complex unsaturated components. The present study focuses on a theoretical investigation of the plausible mechanism in the Fe(OTf)3-catalyzed tandem amidomethylative reactions of α-phenylstyrene. Bis(tosylamido)methane is activated by Fe(OTf)3 to form tosylformaldimine and its Fe(OTf)3-adduct. The Fe(OTf)3-adduct undergoes an intermolecular aza-Prins reaction with α-phenylstyrene to form allylamide. The DFT data support the formation of the hexahydropyrimidine derivative from allylamide, and "condensation/iminium homologation/intramolecular aza-Prins" is the optimal reaction path. At the same time, a possible reaction pathway for the conversion of the hydrolysate 1,3-diamide derivative to the hexahydropyrimidine (HHP) derivative is given. This work is thus instructive for understanding Fe(iii)-based tandem catalysis for the amidomethylative multiple-substitution reactions of alkenes.
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