Diastereodivergent cis - and trans -fused [4 + 2] annulations of cyclic 1,3-dienes and 1-azadienes via ligand-controlled palladium catalysis.

Despite the blossoming of reports of diastereodivergent synthesis over the past years, switchable control of the stereochemistry of the bridgehead atoms of the fused frameworks has been significantly underdeveloped. Here we disclose the ability of Pd 0 -π-Lewis base catalysis to finely reverse the concerted inverse-electron-demand aza-Diels-Alder cycloaddition reaction between cyclic 1,3-dienes and aurone-derived 1-azadienes. In contrast, the in situ -formed HOMO-energy-increased Pd 0 -η 2 -complexes of cyclic 1,3-dienes underwent a cascade vinylogous Michael addition/allylic amination process with 1-azadienes. Moreover, judicious selection of chiral ligands allowed for switchable diastereodivergent [4 + 2] annulations to be accomplished, resulting in the construction of both cis - and trans -fused tetrahydropyridine architectures in high yields with moderate to excellent stereoselectivity levels. A variety of acyclic 1,3-dienes and 1-heterodienes were also applied, and furnished a structural diversity of enantioenriched frameworks.