Pyrrolidines are important heterocyclic compounds with endless applications in organic synthesis, metal catalysis, and organocatalysis. Their potential as ligands for first‐row transition‐metal catalysts inspired a new method to access complex poly‐heterocyclic pyrrolidines in one step from available materials. This fundamental step forward is based on the discovery of an essential organoaluminum promoter that engages unactivated and electron‐rich olefins in intermolecular 3+2 cycloadditions. Trimethylaluminum promotes the first 3+2 azomethine ylide cycloadditions that engage non‐electrophilic olefins. This reaction allows the stereoselective combination of abundant feedstocks to access new polar polydentate scaffolds for ligand design.