Physical Sciences and Mathematics Commons^™

The Development And Expansion Of A Cationic 1,3-Diaza Claisen Rearrangement That Affords Guanidines, Jordan Tocher

Graduate College Dissertations and Theses

Guanidines are found readily in many natural product scaffolds and biological systems. However, the chemical makeup of the guanidines is such that synthesis of guanidine-containing molecules remains challenging. In 2004, the Madalengoitia group first reported a zwitterionic 1,3-diaza Claisen rearrangement that affords complex guanidines. This was later expanded from the initial strained-bridged bicyclic systems to systems that encompassed more linear precursors, positively charged intermediates, and compounds with ring-expansion applications.

Due to the historical precedent that introduction of a positive charge into a rearranging system can benefit the kinetics and thermodynamics of a reaction, experiments were designed in order to probe …