| The focus of this thesis research was to utilize the acylnitroso Diels-Alder reaction to synthesize enantiomerically pure, biologically relevant molecules. If the description of the acylnitroso Diels-Alder cycloadducts as scaffold is accurate, then the cycloadducts are tremendous candidates for solid phase synthesis. Chapter 2 describes the Diels-Alder reactions the acylnitroso species derived from resin bound α-amino hydroxamic acids. The reactions were monitored by gel phase 13C NMR utilizing 13C-labelled L-Ala. While successful, an unidentified resin bound impurity formed in the reaction. The remainder of the thesis concentrated on solution phase functionalization of the cycloadducts.; In chapter 3, the syntheses of highly functionalized diketopiperazines were described that were utilized to differentiate chemically similar dimethyl esters by regioselective cyclization. These diketopiperazines were then utilized to synthesize tripeptide mimetics based on 3,5-dicarbomethoxy-2-oxazole in chapter 4. In addition, an enzyme-mediated reaction differentiated two chemically similar carbomethoxy groups in 2-carbo-tert-butoxy-3,5-dicarbomethoxy-2-oxazole. Aminoxy peptides based on the differentiated oxazole were shown to possess predictable conformations. Methodology was described to completely functionalize the enantiomerically pure oxazole. This should lead to rationally designed conformationally privileged structures.; The final chapter describes the syntheses of either enantiomer of an important 5′norcarbocyclic nucleoside precursor, dioxy-ispropylidene-4-amino( tert-butyloxycarbonyl)-1,2,3-cyclopentanetriol. An important precursor to diaminopimelic acids, 2(S)-amino-6(R)-hydroxy-1,7-heptanedioic acid dimethyl ester hydrochloride was synthesized enatiomerically and diastereomerically pure utilizing the cycloheptadiene derived acyinitroso Diels-Alder reaction. |
