Caractérisation et Propriétés d'Enolates de Cuivre Conjugués – CopEnol

The increasing complexity of target compounds in organic chemistry requires, nowadays, the development of original methodologies which allows to efficient carbon-carbon bond-forming reactions between highly functionalized moieties. Within this perspective, poly-functionalized organometallic species have found great success in synthetic organic chemistry. Although complex scaffolds can be obtained in one-pot via such entities, tuning their reactivity remains a challenge. Thus, mechanistic insights are essential to control, tune and improve regio-, diastereo- and enantio-selectivities. To meet these goals, the combination of three fundamental studies i) physical characterisation of the organometallic species (via NMR analysis); ii) theoretical studies (DFT, ELF); and iii) experimental organic chemistry is crucial. The catalytic and asymmetric vinylogous Mukaiyama reaction is a valuable tool to obtain ', '-unsaturated '-lactones, in a regio-, diastereo- and enantio-controlled way. Despite promising results, mechanistic pathways await further studies. The hypothetical intermediate, possessing both allyl-copper and copper-enolate characteristics, can give, according to subtle reaction conditions modifications, complementary selectivity patterns. It might be possible, by simple changes onto electronic metal character and experimental conditions, to dramatically change selectivities and obtain a versatile tool for organic synthesis. To reach these objectives, the intermediate structure and reaction mechanism must be fully understood. A multidisciplinary approach merging "organic chemistry- NMR and theoretical" studies is thus essential. This project aims to address these objectives by combining means, skills and knowledge on these complementary fields.