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

Abstract

AbstractWe 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.