Development of New Radical Cascades and Multi-Component Reactions, 1st Edition

  • Published By:
  • ISBN-10: 3319013246
  • ISBN-13: 9783319013244
  • DDC: 547.59
  • Grade Level Range: College Freshman - College Senior
  • 326 Pages | eBook
  • Original Copyright 2014 | Published/Released June 2014
  • This publication's content originally published in print form: 2014

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In this dissertation, Marie-Hélène Larraufie develops original radical and pallado-catalyzed methodologies to enable the synthesis of several classes of bioactive nitrogen-containing heterocycles. New radical cascades employing the N-acylcyanamide moiety offer straightforward routes to quinazolinones and guanidines, as well as new insights into the mechanism of homolytic aromatic substitutions. In parallel, Larraufie expands the scope of visible light photoredox catalysis to the ring opening of epoxides and aziridines, thus providing new sustainable alternatives for the generation of radicals. Furthermore, in a collaborative effort with the Catellani group, the author investigates dual palladium/norbornene catalysis. First, she develops a C-amination coupling variant of the Catellani reaction with unprotected amines which provides an expeditious route to phenanthridines. Then, she examines the influence of the chelating effect on Pd(IV) intermediates reactivity with the help of experimental studies and DFT calculations. The work in this thesis has resulted in numerous publications in high impact journals.The clarity and depth of the experimental section will be useful for students and researchers working in this field. 

Table of Contents

Front Cover.
Half Title Page.
Other Frontmatter.
Title Page.
Copyright Page.
Other Frontmatter.
Supervisors’ Foreword.
General Introduction.
1: N-Acylcyanamides as New Partners in Radical Cascades: Synthesis of Polycyclic Quinazolinones and Guanidines.
2: Bibliographical Backgrounds.
3: Results: Developments of New Radical Cascades with N-Acylcyanamides.
4: Supporting Information.
5: Visible-Light Photoreductive Catalysis for an Eco-Compatible Generation of Radicals.
6: Bibliographical Backgrounds: Generation of Radicals by Visible Light Photoredox Catalysis.
7: Results: Visible Light-Induced Photoreductive Generation of Radicals from Epoxides and Aziridines.
8: Supporting Information.
9: New Developments in Aryl–Aryl Couplings Via Palladium/Norbornene Dual Catalysis: Synthesis of Phenanthridines and Phenanthrenes.
10: Bibliographical Background: The Ortho Effect in the Catellani Reaction.
11: Results: New Partners for Ortho-Substituted Aryl Iodides in Palladium/Norbornene Cocatalysis.
12: Supporting Information.
13: General Conclusion.