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Updated: May 21, 2025

Preparation of Contiguous Bisaziridines for Regioselective Ring-Opening Reactions
Published on: July 28, 2022
Enantiomerically Enriched Aziridine-2-carboxylates via Copper-Catalyzed Reductive Kinetic Resolution of 2H-Azirines
Yinuo Zheng1, Elvis Wang Hei Ng2, Antonio Rizzo1
1Department of Chemistry, and State Key Laboratory of Synthetic Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P.R. China.
None:
We present the first reductive kinetic resolution of racemic 2H-azirines to prepare optically enriched N-H aziridine-2-carboxylates, which are bench stable and readily diversifiable building blocks, concomitantly with the corresponding enantiomerically enriched 2H-azirines. The N-H aziridines were obtained with excellent diastereoselectivity (>20:1) and high enantioselectivity (up to 94%). A Hammett study revealed a linear free energy relationship between the ΔΔG⧧ of the diastereomeric transition states and the σp - values. density functional theory (DFT) calculations and non-covalent interaction analysis suggested that non-classical H-bonding interactions and edge-to-face aromatic interactions between the substrate and the ligand are responsible for the stereoselectivity and also for the substrate electronic effects observed in the Hammett study.
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