Adventures with highly reactive enediamines and enetetramines

Rights statement
Awarding institution
  • University of Strathclyde
Date of award
  • 2012
Thesis identifier
  • T13235
Qualification Level
Qualification Name
Department, School or Faculty
  • This thesis makes a contribution to three discrete projects in organic electron transfer chemistry. Chapter 2 investigates the new reactivity of bis-pyridinylidene 1.395. It successfully demonstrates the novel conversion of triflate esters and triflamides to the corresponding alcohols and amines and explores the reaction mechanism,1 and concludes that alkyl triflates are deprotected by a reductive mechanism. Aryl triflates are also deprotected by this reagent, but it is not yet clear whether these reactions are effected by electron transfer or by nucleophile-electrophile chemistry. Chapter 3 showcases the development of two new mono-tethered super-electron-donors 3.34 and 3.42.2 The isolation of these highly reactive tetraazafulvalenes was followed by efforts to prepare the most unstable mono- and non-tethered tetraazafulvalenes 1.309a and 1.309b, respectively via a deprotonation route; this showed NMR evidence of tetraazafulvalene-like molecules, and analysis of these is discussed. In turn, this inspired the successful synthesis and isolation of these compounds within our group by Birch reduction.2 Until now it was believed that mono- and non-tethered imidazole-derived tetraazafulvalenes were too unstable to exist.3,4 Chapter 4 Finally the reactivity of a benzimidazole-derived tetraazafulvalene, 1.275 is reported. This molecule generates aryl radicals from iodoarenes by single electron transfer. The novel reactivity of this benzimidazole-derived super-electron-donor is demonstrated in its application to indole synthesis.
Resource Type
Date Created
  • 2012
Former identifier
  • 947977
Embargo Note
  • The electronic version of this thesis is currently under moratorium due to a licensing issue. If you are the author of this thesis, please contact the Library to resolve this issue.