A switchable dual organocatalytic system and the enantioselective total synthesis of the quadrane sesquiterpene suberosanone.

The combination of aminocatalysis with N-heterocyclic carbene catalysis has been extended to a switchable dual catalytic system, which allowed a direct enantioselective entry to bridged bicyclo[3.n.1] ring systems and the total synthesis of the natural product (1R)-suberosanone.