Rapid Access to Multisubstituted Acrylamides from Cyclic Ketones via Palladium/Norbornene Cooperative Catalysis

Abstract A strategy to access diverse multisubstituted acrylamides from cyclic ketones is realized via palladium/norbornene‐catalyzed α‐carbamoylation and ipso ‐functionalization of the corresponding enol triflates. The development of bulky C2 secondary amide‐substituted norbornene cocatalysts is the key to achieve the desired reactivity and selectivity. Readily available carbamoyl chlorides serve as effective electrophiles; various moieties including alkenyl, hydrogen, alkynyl, aryl, and alkyl groups can be installed at the ipso position. In addition, tandem α‐carbamoylation/ ipso ‐annulations are demonstrated to furnish lactam‐containing polycyclic scaffolds. The utility of this method is exemplified in the streamlined preparation of a platelet‐activating factor (PAF)‐antagonist.