In recent years, our research group has demonstrated that photogeneration of azaxylylenes via ESIPT (Excited State Intramolecular Proton Transfer) provides a straightforward, high yielding pathway to diverse fused quinolinols and azocanes. In this paper we report that this key photochemical step, leading to significant increase of complexity of molecular architectures, could be augmented with robust post-photochemical transformations (here: ground state cycloadditions, such as Povarov reaction or 1,3-dipolar cycloadditions) providing rapid access to elaborate polyheterocyclic scaffolds, shown below. We also explore a number of high yielding coupling reactions for modular assembly of photoprecursors, which provides additional opportunity for diversifying the tether linking the photoactive aminoketone with the furan-based unsaturated pendant allowing for incorporation of additional heterocyclic moieties, such as hydantoins, into the target polyheterocyclic architectures. Utilization of furanacetic acid in place of furanpropanoic acid to install the unsaturated furanyl moiety into the photoprecursor offers a ready path to novel β-lactams fused to the azacane and quinolinol scaffolds. (a) Mukhina, O. A.; Kumar, N. N. B.; Arisco, T. M.; Valiulin, R. A.; Metzel, G. A.; Kutateladze, A. G. Angew. Chem., Int. Ed. 2011, 50, 9423−9428. (b) Kumar, N. N. B.; Mukhina, O. A.; Kutateladze, A. G. J. Am. Chem. Soc. 2013, 135, 9608−9611.

Intramolecular cycloadditions of photogenerated Azaxylylanes as key steps in the diversity-oriented synthesis of novel N,O,S-polyheterocycles

249th National Meeting (2015)

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