Réactions de cycloisomérisation d'ènynes en présence de complexes d'or, de platine et d'ions halogéniums - Approche combinatoire en présence de complexes de platine. Réactions d'acyloxylation par activation C-H d'aromatiques en présence de complexes d'or.

Abstract : This manuscript concerns the development of electrophilic systems, involving gold and platinum π-Lewis acids or halogenium ions and their involvement in C-C triple bond (stereoselective enyne cycloisomerization reactions in the presence or in the absence of an external nucleophile and halocarbocyclization reactions) and C-H bond (acyloxylation reactions of hindered arenes) activation processes. The use of a catalytic system which consists in a binuclear gold (I) complex possessing the diphosphine (R)-4-MeO-3,5-(t-Bu)2C6H2-MeOBIPHEP and a silver salt gives access to methylenecyclopentane derivatives in the presence of an external nucleophile and to bicyclo[4.1.0]heptenes with excellent enantiomeric excesses. This method has been applied to the formal synthesis of the antidepressive agent GSK1360707F. The development of a combinatorial method allowed the fast screening of bidentate ligands/monodentate ligands/Pt systems for stereoselective hydroarylation/cyclization reactions. This methodology has been applied to the screening of ligand combinations for the synthesis of bicyclo[3.1.0]hexanones via a 1,5-enyne cycloisomerization reaction. Switching the metallic complexes with halogenium ions has been realized for halocarbocyclization of 1,5-enynes. Functionalized iodocyclopentenes were synthesized in the presence of NIS in good yields. This method has been applied to a novel approach of constraint analogues of Combretastatin A4. The activation of sp² C-H bonds with (Ph3P)AuCl in the presence of an hypervalent iodine oxidant made possible the direct acetoxy- and acycloxylation of hindered aromatic rings with moderate to good yields.
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Alexandre Pradal. Réactions de cycloisomérisation d'ènynes en présence de complexes d'or, de platine et d'ions halogéniums - Approche combinatoire en présence de complexes de platine. Réactions d'acyloxylation par activation C-H d'aromatiques en présence de complexes d'or.. Chimie organique. Université Pierre et Marie Curie - Paris VI, 2012. Français. ⟨pastel-00832094⟩

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