We describe a novel type of photoclick reaction between 2,3-diaryl indenone epoxide (DIO) and ring-strained dipolarophiles, in which DIO serves as a P-type photoswitch to produce mesoionic oxidopyrylium ylide (PY) to initiate an ultra-fast [5+2] cycloaddition (k2hν =1.9×105 M-1 s-1 ). The photoisomerization between DIO and PY can be tightly controlled by either 365 or 520 nm photo-stimulation, which allows reversion or regeneration of the reactive PY dipole on demand. Thus, this reversible photoactivation was exploited to increase the chemoselectivity of the [5+2] cycloaddition in complex environments via temporal dual-λ stimulation sequences and to recycle the DIO reagent for batch-wise protein conjugation. A dynamic photoswitching strategy is also proposed to compensate for molecular diffusion of PY in aqueous solution, enhancing the spatial resolution of lithographic surface decoration and bioorthogonal labeling on living cells via a spatiotemporal dual-λ photo-modulation.
Keywords: Bioorthogonal Ligation; Cycloadditions; Membranes; Photochromism; Photoclick Reactions.
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