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Substrate-selectivity stemming from recognition is a key feature of enzymes that has been seldom observed in artificial catalysts. Herein, we report a recognition-driven, substrate-selective C–H oxidation that inverts the intrinsic reactivity of the competing C–H bonds. Analysis of this selectivity highlights an unexpectedly high reactivity enhancement imparted by intramolecularity.

Graphical abstract: Enzyme-like substrate-selectivity in C–H oxidation enabled by recognition

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