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Azidoformates are interesting potential nitrene precursors, but their direct photochemical activation can result in competitive formation of aziridination and allylic amination products. Herein, we show that visible‐light‐activated transition‐metal complexes can be triplet sensitizers that selectively produce aziridines through the spin‐selective photogeneration of triplet nitrenes from azidoformates...
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