Development of New Radical Cascades and Multi-Component Reactions

INTRODUCTION.- PART A: N-ACYLCYANAMIDES AS NEW PARTNERS IN RADICAL CASCADES: SYNTHESIS OF POLYCYCLIC QUINAZOLINONES AND GUANIDINES.- THE CYANAMIDE MOIETY, SYNTHESIS AND REACTIVITY.- HOMOLYTIC AROMATIC SUBSTITUTIONS: STATE OF THE ART OF THE MECHANISTIC PROPOSALS.- RESULTS: DEVELOPMENTS OF NEW RADICAL CASCADES WITH N-ACYLCYANAMIDES.- OBJECTIVES OF THE PROJECT.- ADDITION OF ALKYL RADICALS.- ADDITION OF VINYL RADICALS TO N-ACYLCYANAMIDES.- ADDITION OF NITROGEN CENTERED RADICALS.- PREPARATION AND CYCLIZATION OF ALKYL PRECURSORS.- PREPARATION AND CYCLIZATION OF VINYL PRECURSORS.- PREPARATION AND CYCLIZATION OF AZIDE PRECURSORS.- PART B: VISIBLE-LIGHT PHOTOREDUCTIVE CATALYSIS FOR AN ECO-COMPATIBLE GENERATION OF RADICALS.- BIBLIOGRAPHICAL BACKGROUNDS: GENERATION OF RADICALS BY VISIBLE LIGHT PHOTOREDOX CATALYSIS.- PHOTOPHYSICAL PROPERTIES OF TRIS(BIPYRIDYL)RUTHENIUM(II) COMPLEXES.- STATE OF THE ART OF THE SUBSTRATES AMENABLE TO VISIBLE LIGHT PHOTOREDOX CATALYSIS.- RESULTS: VISIBLE LIGHT-INDUCED PHOTOREDUCTIVE GENERATION OF RADICALS FROM EPOXIDES AND AZIRIDINES.- EPOXIDES AS NEW SUBSTRATES FOR VISIBLE-LIGHT TRIGGERED GENERATION OF RADICALS.- SCOPE AND LIMITATIONS OF THE REDUCTIVE RING-OPENING METHODOLOGY.- UTILIZATION OF THE PHOTOGENERATED RADICALS IN CARBON-CARBON BOND FORMATIONS.- SUPPORTING INFORMATION.- GENERAL REMARKS.- GENERAL PROCEDURES.- EPOXIDE, AZIRIDINES AND CYCLOPROPANES PRECURSORS.- REDUCTIVE RING-OPENING PRODUCTS.- ALLYLATION PRODUCTS 246.- PART C: NEW DEVELOPMENTS IN ARYL-ARYL COUPLINGS VIA PALLADIUM/NORBORNENE DUAL CATALYSIS: SYNTHESIS OF PHENANTHRIDINES AND PHENANTHRENES.- BIBLIOGRAPHICAL BACKGROUND: THE ORTHO EFFECT IN THE CATELLANI REACTION.- THE CATELLANI REACTION.- SYNTHETIC APPLICATIONS OF THE ORTHO EFFECT.- MECHANISTIC EXPLANATIONS FOR THE ORTHO EFFECT.- RESULTS: NEW PARTNERS FOR ORTHO-SUBSTITUTED ARYL IODIDES IN PALLADIUM/NORBORNENE COCATALYSIS.- COUPLING OF ORTHO-SUBSTITUTED ARYL IODIDES AND BROMOBENZYL AMINES: FIRST REPORTED CATELLANI

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.