Olefin cross-metathesis (CM) provides a short and convenient entry to diverse trans-γ-aminoenones. When exposed to either acid or Heck arylation conditions, these intermediates are converted to mono-, di-, or trisubstituted pyrroles. The value of this chemistry is demonstrated by its application to the tetrasubstituted pyrrole subunit of Atorvastatin.

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

Copper catalyzed Heck-like cyclizations of oxime esters are described. This new protocol is an effective alternative to Pd-based systems and highlights the value of replacing precious metal catalysts with cheaper and more sustainable variants.

Pd-catalyzed cyclizations of oxime esters with pendant alkenes undergo ligand controlled mechanistic divergence. Electron deficient phosphines promote aza-Heck cyclization; electron rich systems favour a SET pathway. Mechanistic experiments differentiate the two manifolds.