The synthesis of 2-epi-pumiliotoxin C via intramolecular alkene Cope-type hydroamination, and, New routes toward ketonitrones

Abstract

Despite recent advances in the field, the hydroamination methodology has not yet reached its full potential. This thesis focuses on new investigations in Cope-type hydroamination by first examining six-membered ring formation in order to explore and expand the scope of intramolecular Cope-type hydroamination of disubstituted olefins. This objective was achieved by synthesizing pumiliotoxin C (+/-)-3 and its epimer (+/-)-2 through the cyclization of a hydroxylamine precursor (+/-)-1 under transition metal-free reaction conditions.* In the second chapter we discuss the scarcity of methods to make ketonitrones 4 in the current literature and our approach to overcome this constraint using Cope-type hydroamination which involved heating allenes 5 and alkynes 6 with hydroxylamines under metal-free reaction conditions. Improved reaction conditions for the Schiff-base reactions of ketones will also be presented.* *Please refer to dissertation for diagrams.