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We have prepared NHC‐CuI complexes with a rotaxane structure and used them as sterically sensitive catalysts for one‐pot sequential copper‐catalyzed azide/alkyne cycloadditions in solutions containing all of the coupling partners premixed in unprotected form. Most notably, a photolabile and sterically encumbered complex first catalyzed the coupling of a less bulky azide/alkyne pair; after removing...
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