Chemodivergence in Enantioselective Desymmetrization of Diazabicycles: Ring‐Opening versus Reductive Arylation

Divergent bicycle paths: A chemodivergent desymmetrization occurs after an initial enantioselective carbometalation step. The reaction brings a solution to the challenging problem of the enantioselective ring-opening of diazabicyclo2.2.1heptanes to obtain arylated cyclopentenamines (see scheme, right). An alternative reaction pathway was discovered in which CH insertion/1,4-metal migration occurs to give reductive arylation products (left).