Catalytic Chemodivergent Annulations of o‐Aminotrifluoroacetophenone and Allenyl Imide through β’‐C−H Functionalization or β/γ‐Bisfunctionalization

Lewis base and Brønsted base controlled chemodivergent annulations of α‐methyl substituted allenyl imide and o‐aminotrifluoroacetophenones are realized to afford highly valuable furo[3,2‐b]indol‐2‐ones and dihydroquinolines bearing a CF3‐substituted quaternary stereogenic center. The possible reaction mechanisms are proposed through deuterium labelling experiments. This work demonstrates the unprecedented dual reactivities of α‐methyl substituted allenyl imide with electrophilic−nucleophilic compounds in annulation reactions, and features chemodivergence in transforming allenyl imide through β’‐C−H functionalization via phosphine catalysis and β/γ‐bisfunctionalization via Brønsted base catalysis.