Ring the changes: A new photoassisted approach to give conformationally constrained N,O,S-polyheterocyclic scaffolds of unprecedented topologies was achieved by intramolecular [4+4] and [4+2] cycloadditions of photogenerated o-azaxylylenes (23 examples; see scheme). The precursors can be readily assembled by simple and high-yielding reactions, thus making this a powerful synthetic method amenable to high-throughput diversity-oriented synthesis.
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