A new synthetic route to substituted tetracenes and pentacenes via stereoselective [4+2] cycloadditions of 1,4-dihydro-1,4-epoxynaphthalene and isobenzofuran.

Stereoselective [4+2] cycloadditions of 1,4-dihydro-1,4-epoxynaphthalene and isobenzofuran were described. Among several possibilities, syn-exo and/or anti-endo isomers were selectively produced depending on the substitution pattern of the reactants. Importantly, the syn-exo isomer underwent acid promoted aromatization, affording the corresponding tetracene. These findings enabled us to prepare a substituted pentacene with electron withdrawing groups.