Development of peptide-based acyl transfer catalysts and application to the enantioselective synthesis of an aziridinomitosane

Chapter 1. This chapter is a brief survey of the most recent advances in the synthesis of mitosanes, mitosenes, the mitomycin natural products and FR900486. It emphasizes completed total syntheses as well as asymmetric efforts that have culminated in the synthesis of optically pure mitosanes and mitosenes.; Chapter 2. Nucleophile containing amino acids incorporated into short peptide sequences based on beta-turn or beta-hairpin motifs have been found to effect the kinetic resolution of certain alcohols by asymmetric acyl transfer. The design elements, syntheses and results obtained with these catalysts are described in this chapter.; Chapter 3. Application of a small molecule peptide catalyst to the resolution of a key secondary alcohol intermediate in a target-oriented synthesis is described highlighting the screening of a small library of peptide catalysts for identification of this catalyst. Optically pure material obtained from this process was used in an enantioselective synthesis of an aziridinomitosane. Also described herein are two strategies for the total synthesis of mitomycin C as well as the identification of a divergence point for analog synthesis.