The C2 C6 Schmittel cyclization reaction of the benzannulated enyne allenes provides an efficient synthetic pathway for the construction of a variety of polycyclic aromatics. By starting from truxenone, the cascade cyclization reactions furnished several unusual and congested polycyclic compounds. A new synthetic approach to 2,2 -disubstituted 1,1 - binaphthyls and related compounds was also successfully developed using the benzannulated enediynes as precursors. These 1,1 -binaphthyls derivatives can serve as potential BINOL type ligands. The assembly of the enediynyl precursors from three separate aromatic fragments allows the possibility of placing a variety of functional groups at various positions of the 1,1 -binaphthyl system. A 12-step non-pyrolytic synthetic pathway employing the Schmittel cyclization reactions has been developed, leading to a bowl-shaped polycyclic aromatic hydrocarbon (PAH) having a 54-carbon framework of the surface of C60. Incorporating of sp3-carbons on the 54-carbon framework facilitates the connection of carbon atoms intramolecularly.