Application of the efficient [4+4] photocycloaddition of 2-pyridones to natural product synthesis, studied for cyclooctane ring structures, has been adapted to additional polycyclic systems. A [4+4] cycloaddition – [3,3] rearrangement – and retro-Mannich sequence assembles unsymmetrically coupled piperidines with predictable stereochemistry. In a second model study, intramolecular [4+4] cycloaddition of a pyridone and a furan yields a pentacyclic cyclooctadiene. The transannular cyclization of this intermediate can be closed to the tetraquinane framework of the crinipellin.