Synthesis of γ-Aryl Medium-Sized Cyclic Enones by 4π-Electrocyclic Ring-Opening—Heck–Matsuda Arylation Cascade

The ligand free cationic aryl palladium(II) generated from diazonium salt realized transformation of bicyclo[n.2.0]cyclobutenes to γ-aryl medium-sized cyclic enones. The reaction proceeds under room temperature through a capture of cis,trans-cycloalkadiene intermediates, generated via a conrotatory 4π-electrocyclic ring-opening of cis-fused bicyclic cyclobutenes, by Heck–Matsuda arylation. The synthesis of optically pure γ-aryl enone through a point to planar to point chirality transfer process was also demonstrated.