Pd-Catalyzed Rearrangement of N-Alloc-N-allyl Ynamides via Auto-Tandem Catalysis: Evidence for Reversible C-N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement

An auto-tandem catalytic double allylic rearrangement of N-alloc-N-allyl ynamides was developed. This reaction proceeds through two separate and distinct catalytic cycles with both decarboxylative Pd-pi-allyl and Pd(0)-promoted aza-Claisen rearrangements occurring. A detailed mechanistic study supported by computations highlights these two separate mechanisms. Previously unreported reversible C-N ionization and a Pd(0)-catalyzed [3,3]-sigmatropic rearrangement were discovered. This study provides new reaction pathways for both pi-allyl and sigmatropic rearrangements.