DOCTOR OF PHILOSOPHY In the field of Organic Chemistry Application of the Radical Chemistry of Xanthates to the Synthesis of Cyclic or Acyclic Amines
DOCTOR OF PHILOSOPHY In the field of Chimie organique Application of the Radical Chemistry of Xanthates to the Synthesis of Cyclic or Acyclic Amines
Résumé
In chapter 1, general aspects of radical chemistry are briefly introduced. Improvements and applications of the Barton radical decarboxylation, the Barton-McCombie radical deoxygenation and the radical chemistry of xanthates are also described in this chapter. In chapter 2, various methods for the construction of amines and especially radical hydroaminomethylation reaction developed in our group are described. In chapter 3, based on our previous experiences of radical hydroaminomethylation reactions, the synthesis of protected amines, 1,3-diamines, β-aminoacids involving in another radical process, the Wohl-Ziegler reaction, will be described. In chapter 4, a modular approach to access highly complex protected 1,2-diamines via the degenerative transfer of xanthates to protected 1,2-diamino alkenes will be described. Several extensions to prepare mono-protected diamines or indoline bearing diamino-unit will also be mentioned.In chapter 5, we will describe a newly developed modular approach to access highly substituted Boc-protected 4-aminomethyl-pyrroles via a radical addition of various α-xanthyl ketones to Boc-protected azetine following by the aminolysis of adducts. Therefore, plentiful functionalities can be incorporated into the final pyrrole products either through a xanthate partner or through ammonia or a primary amine.
Le travail de thèse de mené par monsieur Songzhe HAN comporte trois parties. La première concerne l’ étude d’un nouvel acces aux amines primaires sous leurs formes protégées par un groupe phtalimide par voie radicalaire. Une voie a été mise au point pour la synthèse du xanthate via une étape de bromation radicalaire au NBS.La deuxième partie concerne l’étude d’un nouvel accès aux diamines sous leurs formes protégées par additions radicalairs. De plus, M. Songzhe Han a rapporté un nouvel accès aux N-Boc 4-aminométhyl-pyrroles via une addition radicalaire de divers xanthates sur l'N –Boc azétine Boc suivie d'une aminolyse des adduits radicalairs obtenus.
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