Development of New Radical Cascades and Multi-Component Reactions

1. Front Matter

   Pages i-xxii

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2. N-acylcyanamides as New Partners in Radical Cascades: Synthesis of Polycyclic Quinazolinones and Guanidines

   1. Front Matter

      Pages 1-1

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   2. Bibliographical Backgrounds

      • Marie-Hélène Larraufie

      Pages 3-37

   3. Results: Developments of New Radical Cascades with N-Acylcyanamides

      • Marie-Hélène Larraufie

      Pages 39-78

   4. Supporting Information

      • Marie-Hélène Larraufie

      Pages 79-136

3. Visible-light Photoreductive Catalysis for an Eco-compatible Generation of Radicals

   1. Front Matter

      Pages 137-137

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   2. Bibliographical Backgrounds: Generation of Radicals by Visible Light Photoredox Catalysis

      • Marie-Hélène Larraufie

      Pages 139-164

   3. Results: Visible Light-Induced Photoreductive Generation of Radicals from Epoxides and Aziridines

      • Marie-Hélène Larraufie

      Pages 165-194

   4. Supporting Information

      • Marie-Hélène Larraufie

      Pages 195-226

4. New developments in Aryl–Aryl Couplings via Palladium/Norbornene Dual Catalysis: Synthesis of Phenanthridines and Phenanthrenes

   1. Front Matter

      Pages 227-227

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   2. Bibliographical Background: The Ortho Effect in The Catellani Reaction

      • Marie-Hélène Larraufie

      Pages 229-255

   3. Results: New Partners for Ortho-Substituted Aryl Iodides in Palladium/Norbornene Cocatalysis

      • Marie-Hélène Larraufie

      Pages 257-293

   4. Supporting Information

      • Marie-Hélène Larraufie

      Pages 295-324

5. Back Matter

   Pages 325-326

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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. 

• Aromatic Homolytic Substitution
• Catellani Reaction
• Cyanamides
• Guanidines
• Ortho Effect
• Palladium IV
• Photoredox Catalysis
• Quinazolinones
• Radical Cascades

• Department of Biological Sciences Department of Chemistry, Columbia University, The Stockwell Labor, New York, USA

  Marie-Helene Larraufie

Marie-Hélène Larraufie graduated in 2008 from École Supérieure de Physique et de Chimie Industrielles (ESPCI-ParisTech). After an M.Sc. in organic and bioorganic chemistry at the Université Pierre et Marie Curie in Paris, she joined the laboratory of Prof. Malacria for her Ph.D. studies. Her doctoral research under the direction of Prof. Fensterbank, Dr. Lacôte and Dr. Ollivier focused on radical chemistry and pallado-catalyzed multi-component reactions. She defended her Ph.D. in 2011 and is now undertaking postdoctoral studies with Dr. B. Stockwell at Columbia University (New York, USA) thanks to a fellowship from Association pour la Recherche sur le Cancer.

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