engleski

Aminonaphthalene Photocages for Carboxylic Acids and Alcohols

Photocages are well-established as applicable tools in organic synthesis and biology [1]. However, a pursuit for an ideal photocage is not over. Particularly important for biological applications is to develop a system undergoing selective and fast photorelease of a substrate, enabling temporal and spatial control of the process. On the contrary, commonly used photocages are derivatives of o-nitrobenzyl alcohols where the decaging takes place slowly in thermal steps that follow the primary photochemistry. Therefore, new molecular systems have to be designed and the photochemical reaction mechanisms that lead to the decaging have to be unraveled. Wang et al. have reported a photocage for alcohols based on the heterolytic cleavage of m-hydroxymethylaniline ethers [2], which was corroborated by a theoretical investigation [3]. We have continued that line of research and prepared a series of ortho-, meta- and para-substituted hydroxymethyl anilines, transformed to ethers or esters 1-3 [4]. We found out that ortho- derivatives show excellent performance in decaging carboxylic acids and meta- for alcohols. Furthermore, we present investigation of the photochemical reactivity for a series of differently substituted aminonaphthalene derivatives 4, where substitution pattern significantly affects the reactivity. Photochemical reactivity of 4 has been studied by irradiations and isolation of photoproducts, fluorescence and laser flash photolysis. The applicability of photocages has been demonstrated for the protection of alcohols or carboxylic acids, which can be used orthogonally with anilines 1 and 2.

aminonaphthalenes ; anilines ; photocages

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