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The development of new bioorthogonal reactions with mutual orthogonality to classic bioorthogonal reactions such as the strain‐promoted azide–alkyne click reaction and the inverse‐electron‐demand Diels–Alder reaction is of great importance in providing chemical tools for multiplex labelling of live cells. Here we report the first anionic cycloaddend‐promoted bioorthogonal cycloaddition reaction between...
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