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Synthèse d'hétérocycles chiraux par catalyse à l'Au(I) et développement de nouveaux phosphahélicènes pour la catalyse énantiosélective

Abstract : Au(I) catalysis is a powerfull tool for heterocycles synthesis, particularly in reactions involving alkynes or allenes. It can be applied both in the synthesis of complex molecules or in the context of total synthesis. During this PhD work, we have developed new chiral Au(I) complexes and new catalytic reactions. We have developed a new family of enantiopure chiral phosphines featuring helicoïdal chirality, obtained by a [2+2+2] cyclotrimerization of alkynes as key step. They have been engaged in late stage functionalization, so as to modify the steric environment and to modify the enantiomeric excess obtained during the catalytic steps. We then studied the phosphine complexation with Au(I) salts. The corresponding phosphahelicenes have been engaged in cycloisomerization reactions. With the best catalyst, a good catalytic activity and an enantiomeric excess of 94 % have been measured. New reactions catalyzed by Au(I) complexes for the synthesis of spiroindolic compounds have been studied, by dearomatizing cyclisation of N-propargyl tryptamines. With this approach, new spirooxindoles and new spiroindolenines have been synthetized. Finally, the enantioselective cycloisomerization of an allenyl pyrrole was studied with chiral Au(I) catalysts. This reaction led to an advanced intermediate, which was converted in few steps to (-)-rhazinilam, a natural product featuring interesting bioactivities. Thus we have described the shortest total synthesis of this natural compound.
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Valentin Magné. Synthèse d'hétérocycles chiraux par catalyse à l'Au(I) et développement de nouveaux phosphahélicènes pour la catalyse énantiosélective. Catalyse. Université Paris-Saclay, 2017. Français. ⟨NNT : 2017SACLS386⟩. ⟨tel-02338414v2⟩

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