The [2.2.2]diazabicyclic indole alkaloids (e.g., brevianamides, stephacidins) originate from a biogenic intramolecular [4+2] cycloaddition with an azadiene derived from an oxidized 2,5-diketopiperazine (pyrazinone) core. We have explored the scope of this reaction in a broad context using inter- and intramolecular cycloaddition with diverse dienophiles. The synthesis of (+)-malbrancheamide B and other natural products will be discussed. [2.2.2]-diazabicyclic structures can also be diverted through a merged cycloreversion process to afford 2-pyridone scaffolds. Our current understanding of cycloreversion process and applications of the chemistry will be detailed. Jonathan Scheerer, College of William and Mary,