This thesis is an investigation of two common misconceptions arising from oversimplifications in undergraduate organic curriculum, as well as the synthesis and metal-catalyzed reactions of C1-substituted oxabenzonorbornadienes. The mechanism of the reaction of secondary alcohols with hydrogen halides is clarified using an explanation of ion pairs, as well as substitution reactions as a mechanistic continuum. Next, the origin of the preferred 'exo' stereochemistry for the Diels-Alder cycloaddition of furan and maleic anhydride is clarified by examining its reaction energetics compared to a prototypical Diels-Alder reaction which follows the Endo Rule. The second part of this thesis is a regiochemical investigation of metal-catalyzed reactions of novel C1-substituted oxabenzonorbornadienes, prepared via Diels-Alder reactions (16-80%). Ruthenium-catalyzed isomerization results in the 4-substituted-1-naphthol (71->99%) for alkyl and aryl substituents, while 1-substituted-2-naphthol is the major product (68%) for an electron-withdrawing substituent. Rhodium-catalyzed phenylboronic acid addition resulted in the ' cis'-4-substituted-2-phenyl-1,2-dihydronaphthalen-1-ol regioisomer (54-95%).