Thèse soutenue

Nouvelles synthèses à partir d'éléments de construction basés sur le squelette 1,3-butadiényle et nouveaux catalyseurs du ruthénium pour l'allylation régiosélective
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Auteur / Autrice : Hui-Jun Zhang
Direction : Christian BruneauZhenfeng Xi
Type : Thèse de doctorat
Discipline(s) : Chimie
Date : Soutenance en 2010
Etablissement(s) : Rennes 1 en cotutelle avec Université de Pékin
Ecole(s) doctorale(s) : École doctorale Sciences de la matière (Rennes ; 1996-2016)
Partenaire(s) de recherche : autre partenaire : Université européenne de Bretagne (2007-2016)

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Résumé

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In this thesis the author concentrates on the preparation of several novel building blocks based on butadienyl skeleton and their synthetic application for organic synthesis. Stereo-defined 1,1,4,4-tetrahalo-1,3-butadienes could be readily synthesized. The reactions of these butadienes with butyllithium and its Suzuki coupling reactions with aryl boronic acid are unprecedented. Moreover, bis(pinacolato)diboron could react with 1,4,4-trihalo-1-lithiodienes which were obtained in situ by lithiation of our new bis(gem-dihalo)dienes, to afford corresponding novel gem-diboryldienes which serve as good substrates for the Miyaura-Suzuki coupling reaction. Upon treatment with LiAlH₄, 1,4-dicyano-1,4-bis(trimethylsilyl)-1,3-dienes could undergo a novel hydride-induced cyclization to afford multiply functionalized cyclopentadienes in high isolated yields. In a second objective, novel [Ru(C₅Me₄R)(2-quinolinecarboxylato)(CH₂CHCHR')][PF6] and [Ru(C₅Me₅)(2-quinolinecarboxylato)(CH₂CHCHn-Pr)][BF₄], allyl ruthenium(IV) complexes were synthesized. These complexes were used as catalysts in allylation reactions, and it is the first time that high regioselectivity in favor of the branched product was obtained from purely aliphatic allylic substrates and functional vinylsilanes.