Synthesis of chiral (R)-4-hydroxy- and (R)-4-halogeno[2.2]paracyclophanes and group polarizability: optical rotation relationship

A novel method for the synthesis of (R)-4-hydroxy-, -4-fluoro, -4-bromo and -4-iodo[2.2]paracyclophanes was developed based on the utilization of (R)-(-)-4-amino[2.2]paracyclophane. The synthetic strategy was characterized by the generation of (R)-(-)-4-amino[2.2]cyclophane by the metalation of (R)-(-)-4-bromo[2.2]paracyclophane with n-butyllithium and successive animation of the resulting 4-lithio derivative. The target compound was also obtained by the alkaline hydrolysis of (R)-4-acetoxy[2.2]paracyclophane which was derived from the intermediate product.