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New Reagents for Fluoroalkylchalcogenations : Applications to Hot Chemistry Ermal Ismalaj

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New Reagents for Fluoroalkylchalcogenations : Applications to Hot Chemistry Ermal Ismalaj New Reagents For Fluoroalkylchalcogenations : applications To Hot Chemistry Ermal Ismalaj To cite this version: Ermal Ismalaj. New Reagents For Fluoroalkylchalcogenations : applications To Hot Chemistry. Or- ganic chemistry. Université de Lyon, 2017. English. NNT : 2017LYSE1021. tel-01522960 HAL Id: tel-01522960 https://tel.archives-ouvertes.fr/tel-01522960 Submitted on 15 May 2017 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. N°d’ordre NNT : 2017LYSE1021 THESE de DOCTORAT DE L’UNIVERSITE DE LYON opérée au sein de l’Université Claude Bernard Lyon 1 Ecole Doctorale ED 206 (Ecole Doctorale de Chimie) Spécialité de doctorat : Chimie Discipline : Chimie Organique Soutenue publiquement 10/02/2017, par : (Ermal Ismalaj) New Reagents For Fluoroalkylchalcogenations. Applications To Hot Chemistry Devant le jury composé de : Popowycz Florence Professeur INSA Lyon Présidente Gouverneur Véronique Professeur University of Oxford Rapporteur Magnier Emmanuel, DR CNRS Université de Versailles-Saint-Quentin Rapporteur Zimmer Luc, Professeur, Université Claude Bernard Lyon-1, Examinateur Billard Thierry DR CNRS Université Lyon 1 Directeur de thèse Le Bars Didier, MCU-PH, Universite Lyon 1. Membre invite UNIVERSITE CLAUDE BERNARD - LYON 1 Président de l’Université M. le Professeur Frédéric FLEURY Président du Conseil Académique M. le Professeur Hamda BEN HADID Vice-président du Conseil d’Administration M. le Professeur Didier REVEL Vice-président du Conseil Formation et Vie Universitaire M. le Professeur Philippe CHEVALIER Vice-président de la Commission Recherche M. Fabrice VALLÉE Directeur Général des Services M. Alain HELLEU COMPOSANTES SANTE Faculté de Médecine Lyon Est – Claude Bernard Directeur : M. le Professeur J. ETIENNE Faculté de Médecine et de Maïeutique Lyon Sud – Charles Directeur : Mme la Professeure C. BURILLON Mérieux Directeur : M. le Professeur D. BOURGEOIS Faculté d’Odontologie Directeur : Mme la Professeure C. VINCIGUERRA Institut des Sciences Pharmaceutiques et Biologiques Directeur : M. le Professeur Y. MATILLON Institut des Sciences et Techniques de la Réadaptation Directeur : Mme la Professeure A-M. SCHOTT Département de formation et Centre de Recherche en Biologie Humaine COMPOSANTES ET DEPARTEMENTS DE SCIENCES ET TECHNOLOGIE Faculté des Sciences et Technologies Directeur : M. F. DE MARCHI Département Biologie Directeur : M. le Professeur F. THEVENARD Département Chimie Biochimie Directeur : Mme C. FELIX Département GEP Directeur : M. Hassan HAMMOURI Département Informatique Directeur : M. le Professeur S. AKKOUCHE Département Mathématiques Directeur : M. le Professeur G. TOMANOV Département Mécanique Directeur : M. le Professeur H. BEN HADID Département Physique Directeur : M. le Professeur J-C PLENET UFR Sciences et Techniques des Activités Physiques et Sportives Directeur : M. Y.VANPOULLE Observatoire des Sciences de l’Univers de Lyon Directeur : M. B. GUIDERDONI Polytech Lyon Directeur : M. le Professeur E.PERRIN Ecole Supérieure de Chimie Physique Electronique Directeur : M. G. PIGNAULT Institut Universitaire de Technologie de Lyon 1 Directeur : M. le Professeur C. VITON Ecole Supérieure du Professorat et de l’Education Directeur : M. le Professeur A. MOUGNIOTTE Institut de Science Financière et d'Assurances Directeur : M. N. LEBOISNE Abbreviations GENERAL INTRODUCTION .......................................................................................... 1 CHAPTER I: Synthesis of SCF2R derivatives and their application in electrophilic reactions. I. BIBLIOGRAPHY SCF3 AND SCF2R ........................................................................... 10 I.1 INDIRECT INSERTION OF SCF3 GROUP: ..................................................................................... 10 I.1.1 Radical trifluoromethylation of thiols, thiolates and disulfides. .................................... 10 I.1.2 Electrophilic trifluoromethylation of thiols and thiolates. ............................................. 12 I.1.3 Nucleophilic trifluoromethylation of thiols, thiolates and disulfides. ........................... 13 I.2 DIRECT INSERTION OF SCF3 GROUP ......................................................................................... 15 I.2.1 Radical trifluoromethylthiolation reactions ....................................................................... 15 I.2.1.1 Trifluoromethanethiol and trifluoromethanesulfenyl chloride ............................................. 15 I.2.1.2 Trifluoromethylthiosilver (I) ...................................................................................................... 16 I.2.1.3 N- and O- trifluoromethylthiolating reagents ......................................................................... 18 I.2.2 Nucleophilic trifluoromethylthiolation reactions ............................................................. 19 I.2.2.1 Difluorothiophosgene ................................................................................................................. 19 I.2.2.2 Mercury (II) trifluoromethylthiolate ......................................................................................... 19 I.2.2.3 Trifluoromethylthiosilver (I) ...................................................................................................... 20 I.2.2.4 Trifluoromethylthiocopper (I) ................................................................................................... 23 I.2.2.5 Trifluoromethylthio ammonium/cesium ................................................................................. 25 I.2.2.6 S8 and ¯CF3 anion ........................................................................................................................ 27 I.2.2.7 O-Octadecyl-S-trifluorothiolcarbonate .................................................................................... 28 I.2.2.8 Trifluoromethanesulfenamides used in nucleophilic reaction .............................................. 29 I.2.3 Electrophilic trifluoromethylthiolation reactions ............................................................. 30 I.2.3.1 Trifluoromethanesulfenyl chloride and bis-trifluoromethyl disulfide ................................. 30 I.2.3.2 Trifluoromethanesulfenamides .................................................................................................. 31 I.2.3.3 N-Trifluoromethylthiophtalimide and N-trifluoromethylthiosuccinimide ........................ 34 I.2.3.4 Trifluoromethylsulfenate reagents ............................................................................................ 36 I.2.3.5 N-Trifluoromethylthiosaccarin .................................................................................................. 37 I.2.3.6 Trifluoromethanesulfenyl hypervalent iodonium ylide .......................................................... 39 I.2.3.7 Trifluoromethylthiosilver (I) as an electrophilic reagent ....................................................... 39 I.3 S-CF2H AND S-CF2FG BOND FORMATION; INDIRECT APPROACH ........................................ 41 I.3.1 Difluoromethylation with difluorocarbene sources ......................................................... 41 I.3.1.1 ClCF2H as a difluorocarbene source ........................................................................................ 41 I.3.1.2 CF2Br2 and ClCF2Br as difluorocarbene sources ................................................................... 42 I.3.1.3 SCDA, PDFA and TFDA as difluorocarbene sources ......................................................... 43 7 I.3.1.4 Diethyl bromodifluoromethylphosphonate and Difluoromethyltri(n-butyl)ammonium chloride ........................................................................................................................................................ 44 I.3.1.5 HCF3, TMSCF2Br and HCF2OTf as difluorocarbene sources ............................................ 44 I.3.1.6 N-Tosyl-S-difluoromethyl-S-phenylsulfoximine as a difluorocarbene source ................... 45 I.3.2 Radical Difluoromethylation ............................................................................................... 45 I.3.2.1 DFMS, ICF2COOEt; new reagents for radical difluoromethylation .................................. 46 I.3.3 Nucleophilic difluoromethylation of disulfides ................................................................ 46 I.3.3.1 Difluoromethyl trimethylsilane, difluoromethyl phenyl sulfone and α- fluorodiaroylmethanes ................................................................................................................................ 46 I.3.3.2 (NHC)Ag(CF2H) in nucleophilic difluoromethylations ........................................................ 47 I.3.4 Electrophilic difluoromethylation of thiols and thiolates ............................................... 48 I.3.4.1 Rupert-Prakash reagent and a sulfoximine derivative used in electrophilic difluoromethylation ..................................................................................................................................... 48 I.3.4.2 Hypervalent
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