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

• DOI: 10.1021/acs.orglett.0c04078
• Publication Date: 2021-01-10T09:35:20Z
• Authors: Juliana R. Alexander; Veronika I. Shche...; Ksenia S. Stankevich; Rory J. Benedict; Samuel P. Bernhard; Reagan J. Dreiling; Matthew J. Cook
• Keywords: Ketenimine; Tandem

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