Intramolecular photoassisted cycloadditions of azaxylylenes and postphotochemical capstone modifications via Suzuki coupling provide access to complex polyheterocyclic biaryls.

Modular preassembly of azaxylylene photoprecursors, halogen-substituted in the aromatic ring, their intramolecular [4 + 4] or [4 + 2] cycloadditions to tethered unsaturated pendants, and subsequent postphotochemical capstone modification of the primary photoproducts via Suzuki coupling provides rapid access to diverse biaryls of unprecedented topology. This synthetic sequence allows for rapid growth of molecular complexity and is well aligned with methodology of Diversity-Oriented Synthesis.