UC Irvine

The first chapter of this thesis illustrates the application of kinetic resolution reagents for determining the absolute configuration. This method utilizes each enantiomer of the kinetic resolution reagent in parallel reactions with the epoxide of interest. The competing enantioselective conversion (CEC) method was initially applied to cyclic six-membered epoxides using 1H NMR to monitor the conversion of the reactions. The substrate scope was explored with more complex epoxides, as well terminal epoxides. The CEC method was based on a chiral lithium-diamide base. The synthesis of both enantiomers of the diamine base, the substrate scope, and the difficulties encountered will be discussed.

The second chapter discusses the attempt to develop a colorimetric method to use with the competing enantioselective conversion method. This method was meant to compliment the already existing 1H NMR, TLC, and mass spectrometry detection methods. Aromatic bases and aromatic acyl sources were initially explored, followed by acetate anion sensors and pH sensors. The CEC method that was used to study these colorimetric options was the acylation of secondary alcohols with the chiral acyl-transfer reagent homobenzotetramisole (HBTM).

Chapters 3–5 discuss the Lycopodium alkaloids and the development of a unified approach to synthesizing several members of this family of natural products. The third provides an overview of the past syntheses of select molecules of interest. The fourth chapter discusses the use of computer modeling in inspiring a second-generation approach to a molecule previously synthesized by our group: (+)-fastigiatine. The fifth, and final chapter, provides the groundwork for a unified approach to synthesizing lyconadin A–E. The screening of conditions, the challenging steps, and the current progress will be discussed.