The preparation of a novel cytochrome P-450 photoaffinity label is described. The targeted azidoquinone was to be used as a photo-reactive label to specifically identify peptides associated with the oxidation binding site within cytochrome bc1, and consequently determine the unique catalytic mechanism of quinol oxidation processes and the intermediates involved. The synthetic route features a Diels-Alder cyclization/alkylation/decyclization approach to prepare the mimic of naturally occurring ubiquinone. The synthesis is accomplished in 6 steps from commercially available 4-methylcatechol and involves incorporation of azide in the final synthetic step to prepare the novel azidoquinone. (S)–Wynberg lactone was used to prepare the potent CERT inhibitor (1R,3S)-HPA-12. The route featured the preparation of an optically active azidolactone through a Corey-Link reaction accompanied by nucleophilic acyl substitution. The synthesis was accomplished in 5 steps, and proceeded in 33% overall yield from (S)–Wynberg lactone. (R)-Wynberg lactone was used to prepare chiral polysubstituted oxacycles through a novel Jocic-type reaction. The route featured a directed 1,3-reduction of a β-hydroxyketone followed by ruthenium-catalyzed cross metathesis and osmium-catalyzed asymmetric dihydroxylation. A modified olefin metathesis procedure to suppress undesired byproduct formation is described in detail. A variety of functionalized olefins were prepared by the modified procedure in yields commonly exceeding 80%. Functionalized tetraols were prepared by a modified Sharpless asymmetric dihydroxylation reaction with yields commonly exceeding 80%, and diastereomeric ratios typically exceeding 85:15. Stereoselectivity in the dihydroxylation of terminal mono-substituted olefins can be enhanced with a pre-formed phenyl boronic ester adduct. Conditions for enhancing the stereoselectivity with this class of substrates are described in detail. The final synthetic step en route to the targeted tetrahydopyran derivatives involves intramolecular cyclization through a novel Jocic-type reaction, and commonly proceeds in > 80% yield. Work towards the cyclization of all classes of prepared tetraols is currently in progress. Terminal alkylsulfanyl alcohols were prepared in one step from an aliphatic trichloromethyl carbinol in yields exceeding 85%. These results further demonstrate the utility of gem-dichloroepoxide intermediates in Jocic-type reactions, and lay the groundwork for future transformations. Work in this area is currently underway.