Abstract A novel method for construction of biaryls via palladium (0)-catalyzed [2+ 2+ 2] cocyclization of diynes and arynes was developed. By this [2+ 2+ 2] cocyclization, various arylnaphthalene derivatives, including a sterically hindered 2, 2′-disubstituted-1, 1′- binaphthyl, can be constructed by virtue of a variety of combinations of diynes and aryne precursors. Using this [2+ 2+ 2] cocyclization as a key step, the total syntheses of natural ...