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Diverse photocycloaddition pathways have been found in the photocycloaddition of α-diketones with different C=C species.[1] Using the combination of photocycloadditions with subsequent transformation reactions, structurally diversified heterocycles have been constructed with high efficiency and selectivity.[2] Polycyclic molecules with activity to regulate endogenous microRNAs have been screened from the photocycloadducts.[3] Some of the photocycloaddition with fast reaction kinetics and fluorescence turn-on properties hold the potential to serve as bio-orthogonal photo-ligation reactions.