The scope and mechanism of aza-Heck methodologies that provide chiral heterocyclic systems are outlined.

Aza-Heckc yclizations initiated by oxidative addition of Pd 0 -catalysts into the N À Ob ond of N-(pentafluorobenzoyloxy)sulfonamides are described. These studies,w hich encompass only the second class of aza-Heck reaction developed to date,p rovide direct access to diverse N-heterocyclic ring systems.

Pd­(0)-systems modified with SPINOL-derived phosphoramidate ligands promote highly enantioselective aza-Heck cyclizations of alkenyl N-(tosyloxy)­carbamates. The method provides versatile access to challenging N-heterocycles and represents the broadest scope enantioselective aza-Heck protocol developed to date.

Ligand‐enabled aza‐Heck cyclizations and cascades of N‐(pentafluorobenzoyloxy)carbamates are described. These studies encompass the first examples of efficient non‐biased 6‐exo aza‐Heck cyclizations. The methodology provides direct and flexible access to carbamate protected pyrrolidines and piperidines.

Structurally complex benzo-and spiro-fused N-polyheterocycles can be accessed via intramolecular Pd(0)-catalyzed alkene 1,2-aminoarylation reactions. The method uses N-(pentafluorobenzoyloxy)carbamates as the initiating motif, and this allows aza-Heck-type alkene amino-palladation in advance of C−H palladation of the aromatic component. The chemistry is showcased in the first total synthesis of the complex alkaloid (+)-pileamartine A, which has resulted in the reassignment of its absolute stereochemistry.