Oxabicyclic alkenes have been the focus of many synthetic studies as they are versatile compounds which act as synthetic intermediates to produce a variety of useful heterocyclic, carbocyclic and acyclic products. The nucleophilic ring opening reaction of oxabenzonorbornadiene was studied. Methanol was the primary nucleophile used throughout the investigation, however various other alcohol nucleophiles were also tested for their efficacy. The effects of substitution were explored, providing ring opened products in yields of up to 81%. The [2+2] cyclodimerization reaction of oxanorbornadienes was also examined providing the first examples of dimers of this kind. The scope was expanded to include other 2,3-diester oxanorbornadienes as well as various C1 substitutions. Changing the ester moiety did not affect the reaction, however the addition of a C1 alkyl substituent did result in lower yields. Moderate yields of up to 66% were obtained. Additionally, a new ruthenium complex was discovered in the process.

This report is an investigation of regioselectivity in transition metal catalyzed ring-opening reactions involving unsymmetrical oxabicycles, specifically with a substituent at the C1 position. This report also provides the details of the work conducted towards the preparation of various oxanorbornadienes and their precursors. A large number of reactions have been developed using various transition metal catalysts on oxabicyclic alkenes to form functionalized organic scaffolds. However, most of the literature is limited to symmetrical substrates. Introduction of a substituent at the bridgehead carbon of the bicyclic ring makes the molecule unsymmetrical. The implications of loss of the plane of symmetry in C1 substituted oxabicyclic ring are manifested in interesting ways during various metal catalyzed reactions. The fundamental basis for the current work is to study the consequences of transition metal catalyzed ring opening reactions of unsymmetrical bicyclic alkenes. The reactivity of a wide range of C1 substituted benzoxanorbornadienes and oxanorbornadienes in palladium and nickel-catalyzed ring opening reactions was explored. The palladium catalyzed ring opening reaction of both electron rich and electron deficient C1 substituted benzoxanorbornadienes are optimized. The ring opening reactions with electron withdrawing C1 substituent resulted in formation of substituted naphthalene-1-carboxylic acid methyl ester derivatives in up to 85% yield. Electron donating substituents on the C1 position of benzoxanorbornadiene led to the formation of substituted cis-1,2-dihydronaphthol rings in excellent yields. Palladium catalyzed ring opening reactions were also explored with a wide range of aryl iodides and halobenzenes. The electronic and steric effects of the substituent at the C1 position of oxabicyles were also investigated. The nickel catalyzed ring opening reactions resulted in formation of inseparable regioisomeric mixtures of products. However, it was found that the nickel catalyzed ring opening of 1-methoxycarbonyl-7-oxabenzonorbornadiene occurred regioselectively affording a single product. A scalable procedure for preparation of large quantities of 2-bromofuran was developed. 2-Aryl furans were prepared using Suzuki cross coupling protocols of 2-bromofuran with aryl boronic acids whereas 2-alkyl furans were prepared by iron catalyzed cross coupling reaction of 2-bromofuran with various alkyl and cycloalkyl Grignard reagents. The 2-substituted furans were used for the preparation of novel C1 substituted benzoxanorbornadiene and oxanorbornadienes.