Transient N-Aziridinyl Radicals in Olefin Functionalization

Abstract

Aziridines are the smallest nitrogen-containing heterocycles and are responsible for the biological activity of aziridine-natural products and active pharmaceutical ingredients (APIs). Classically, aziridines are prepared from acyclic precursors via 1) [2+1] cycloaddition of a nitrene equivalent with an olefin, 2) [2+1] cycloaddition of a carbene equivalent with an imine, or 3) via intramolecular cyclization of β-functionalized amines. In comparison, introduction of intact aziridines is an uncommon disconnection. Here, we highlight the recent development of N-aziridinyl radicals as novel intermediates in synthetic chemistry that enable olefin hydroxyaziridination. These intermediates, generated by photoredox activation of N-pyridinium aziridine precursors, afford access to products of a heretofore unknown epoxide opening with N-aziridine nucleophiles and introduce new disconnections of olefin aziridination chemistry.

1 Introduction

2 Classical Aziridination Methods

3 Aziridine-Group Transfer

4 Conclusions

Key words

aziridines - olefin functionalization - nitrogen-centered radicals - N-aminopyridinium salts

Publication History

Received: 10 March 2025

Accepted after revision: 16 April 2025

Accepted Manuscript online:
16 April 2025

Article published online:
12 June 2025

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