UCLA

In Chapter 1, the syntheses of 2'-fluoro-N-methanocarbathymidine (2'F-NMC) and arabino 2'-fluoro-N-methanocarbathymidine (ara-2'F-NMC) are detailed. The syntheses of both molecules begin with the simple precursor cyclopenten-1-one. Asymmetry is introduced into the molecule by means of a Corey-Bakshi-Shibata asymmetric reduction. The cyclopropane was installed using a directed Simmons-Smith cyclopropanation reaction. The Michael addition of dibenzylamine with the fluoroenone was observed with good diastereoselectivity. The biological activity of the monomer incorporated oligonucleotides will also be discussed.

In Chapter 2, multiple approaches towards a synthesis of morphine were attempted. A palladium-catalyzed Tsuji-Trost reaction will be featured as an attempt to form the C-ring of morphine's carbon framework. A new palladium-catalyzed cyclopropanation reaction to form vinylcyclopropyl ketones was discovered during this pursuit. Another approach towards synthesizing morphine will feature an attempt to form the C-ring by means of a Diels-Alder reaction. The last approach discussed, will be an attempted oxy-Cope rearrangement reaction to potentially install the quaternary center of morphine.