Lepage Mathieu L, Gras Emmanuel
Laboratoire Hétérochimie Fondamentale et Appliquée (UMR 5069), CNRS / Université de Toulouse, 118 route de Narbonne, 31062, Toulouse, France.
Chemistry. 2025 Aug 1;31(43):e202500414. doi: 10.1002/chem.202500414. Epub 2025 Jul 11.
Diazirines are 3-membered heterocycles containing two nitrogen atoms connected by a double bond. They are mostly known for their usage in photoaffinity labeling (PAL), due to their stability and their facile photolysis for on-demand carbene generation. Yet diazirines possess a multi-faceted reactivity that also holds great potential for organic synthesis. This is illustrated in the present review, which is meant to be a beginner's guide for new diazirine users. After briefly summarizing the main synthetic approaches to these derivatives (with a focus on recent improvements), we emphasize some of their most critical features and properties before describing the various modes of activation toward carbene generation, some of which were only uncovered in the past decade. We then review the many modern uses of diazirines, underlining their underappreciated versatility: as carbene precursors in synthesis, but also as electrophilic nitrogen donors, as NMR hyperpolarization probes, or as molecular tools in materials science.
重氮丙环是含有通过双键连接的两个氮原子的三元杂环。它们主要因其在光亲和标记（PAL）中的应用而闻名，这归因于它们的稳定性以及易于光解以按需生成卡宾。然而，重氮丙环具有多方面的反应性，这在有机合成中也具有巨大潜力。本综述对此进行了阐述，旨在为新的重氮丙环使用者提供入门指南。在简要总结这些衍生物的主要合成方法（重点关注近期的改进）之后，我们在描述生成卡宾的各种活化模式之前，强调了它们一些最关键的特征和性质，其中一些是在过去十年才发现的。然后，我们回顾了重氮丙环的许多现代用途，强调了它们未被充分认识的多功能性：作为合成中的卡宾前体，也作为亲电氮供体、核磁共振超极化探针或材料科学中的分子工具。
