The reaction of rhodium enalcarbenoids with α-amino ketones has led to the discovery of chemodivergent [3+3] annulations. Acyclic α-amino ketones reacted via a protic ammonium ylide resulting in 1,2-dihydropridines (1,2-DHPs). In contrast, cyclic α-aminoketones gave fused 1,4-oxazines via a vinylogous protic ammonium ylide due to a topology-driven regioselectivity switch. The 1,2-DHP and 1,4-oxazine products serve as precursors to diverse N-heterocycles. More information can be found in the Research Article by P. K. Mandal and S. Katukojvala (DOI: 10.1002/chem.202303862).