Work

Enantiomerically Enriched Aziridine‐2‐carboxylates via Copper‐Catalyzed Reductive Kinetic Resolution of 2 H ‐Azirines

Year: 2025

Type: article

Abstract: We present the first reductive kinetic resolution of racemic 2 H ‐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 2 H ‐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 σ p − 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.

Source: Angewandte Chemie

DOI: 10.1002/ange.202423645

Authors: Yinuo Zheng, Elvis Wang Hei Ng, Antonio Rizzo, Pauline Chiu

Institutions: State Key Laboratory of Synthetic Chemistry, University of Hong Kong

Language: English

Topic: Synthesis and Catalytic Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,790

Funders: Innovation and Technology Commission, Hong Kong Government