A series of substituted 9-methylenylanthracene
photocages for diphenylphosphinothioesters
have been synthesized to explore their photo-uncaging properties by
visible light. Substituents such as phenyl, p-trifluoromethylphenyl, p-methoxyphenyl, ethyn-1-ylbenzene, and 3,3-dimethylbut-1-yn-1-yl
have been introduced in order to extend the π-conjugation of
the photocage and to shift the wavelength response of the uncaging
process to the visible spectral range. Among these new photocages,
the (10-(3,3-dimethylbut-1-yn-1-yl)anthracen-9-yl)methyl has been
shown to have the best performance in terms of fast photo-uncaging
and minimal byproduct formation. It is responsive to both UV and visible
photoexcitation. Quantum yields of the photoinduced heterolytic anthracenylmethyl–phosphorus
bond cleavage at 366 and 416 nm were found to be 0.08 and 0.025, respectively.
This photocage enables traceless Staudinger ligation to be triggered
by photoirradiation in the visible spectral range for bioconjugation
applications. We demonstrate this with a series of visible-light-induced
oligopeptide syntheses via the conjugation of amino acid/oligopeptide
building blocks by the characteristic peptide linkage attained by
traceless Staudinger ligation. Yields of the resultant conjugated
oligopeptides ranged from 31 to 43%. This new photocage opens up the
possibility of in situ synthesis of functional proteins/peptides mediated
by visible-light-induced photoclick processes for the regulation of
cellular/metabolic functions of life systems.
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