Palladium-Catalyzed Double Carbonylative Cyclization of Benzoins: Synthesis and Photoluminescence of Bis-Ester-Bridged Stilbenes

A palladium-catalyzed double carbonylative cyclization of benzoins has been developed, which realizes the synthesis of bis-ester-bridged stilbenes just in two steps from aldehydes. Thus, the obtained fully fused tetracyclic pi-systems have a pyrano[3,2-b]pyran-2,6-dione (PPD) core on their center, showing two reversible reductions at low potentials. In addition, their photoluminescence properties are strikingly affected by the aromatic rings fused to the PPD core; bis-thieno-fused PPDs are found to be excellent fluorophores with quantum yields up to 0.98.