Pd-Catalyzed Rearrangement of <i>N</i>-Alloc-<i>N</i>-allyl Ynamides <i>via</i> Auto-Tandem Catalysis: Evidence for Reversible C–N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement
Juliana R. Alexander, Veronika Shchepetkina, Ksenia S. Stankevich, Rory J. Benedict, Samuel P. Bernhard, Reagan J. Dreiling, Matthew J. Cook
Abstract
-allyl ynamides was developed. This reaction proceeds through two separate and distinct catalytic cycles with both decarboxylative Pd-π-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 π-allyl and sigmatropic rearrangements.
Topics & Concepts
KetenimineChemistryCatalysisTandemClaisen rearrangementMedicinal chemistryCombinatorial chemistryOrganic chemistryMaterials scienceComposite materialCatalytic Alkyne ReactionsCyclopropane Reaction MechanismsCatalytic Cross-Coupling Reactions