Enantioselective Construction of Eight‐Membered N‐Heterocycles from Simple 1,3‐Dienes via Pd(0) Lewis Base Catalysis

Abstract We report herein an unprecedented enantioselective (4+4) cycloaddition of simple 1,3‐dienes with azadienes for the construction of fused eight‐membered N ‐heterocycles. In this transformation, the π‐Lewis basic Pd(0) catalyst achieves activation of 1,3‐dienes to induce nucleophilic addition to azadienes followed by ring cyclization via a selective terminal allylic substitution. Furthermore, highly efficient and diastereoselective derivatizations of the eight‐membered rings provide a facile access to diverse enantiopure fused tetra‐ to hexacyclic compounds with potential application in medicinal chemistry.