Nucleophilic ring opening of oxabenzonorbornadiene (OBD) has been used in natural product synthesis as it enables precise creation of multiple stereocenters in a single step. The work presented in this thesis investigates how modifications to the OBD framework influences the regio- and stereochemistry of the products. The scope of the nickel catalyzed arylation of OBD was broadened by including C1-substituted substrates. Different 1,2-dihydronaphthol or naphthalene regioisomers could be obtained by varying the substituents’ electronic properties. The latter chapters focus on the ring opening chemistry of OBD derivatives. Intramolecular ring opening of OBD was explored through the synthesis of OBDs with C1-tethered nucleophiles. Subsequent ring opening of these compounds yielded tricyclic and tetracyclic products. Finally, the scope of the palladium catalyzed Type 2 ring opening and the acid catalyzed Type 3 ring opening of the OBD derivative, cyclopropanated oxabenzonorbornadiene (CPOBD), was expanded to include substituted CPOBD substrates.