| Title: |
Synergistic gold/silicon catalysis by activation of organosilanes and hydrosilanes using Au(I) complexes : developments and applications ; Catalyse synergique οr/silicium par activatiοn d’οrganοsilanes et d’hydrοsilanes au mοyen de cοmplexes d’Au(Ι) : dévelοppements et applicatiοns |
| Authors: |
Pascaretti, Mathieu |
| Contributors: |
Unité de Recherche en Chimie Organique et Macromoléculaire (URCOM); Université Le Havre Normandie (ULH); Normandie Université (NU)-Normandie Université (NU); Normandie Université; Vincent Dalla; Patrick Pale |
| Source: |
https://theses.hal.science/tel-04887424 ; Chimie. Normandie Université, 2024. Français. ⟨NNT : 2024NORMLH01⟩. |
| Publisher Information: |
CCSD |
| Publication Year: |
2024 |
| Collection: |
Normandie Université: HAL |
| Subject Terms: |
Organometallic chemistry; Gold/silicon catalysis; Au(I) complex; Catalyse or/silicium; Complexe d’Au(I); C-glycosylation; Glycosides; Glycals; Alcynylation; [CHIM]Chemical Sciences |
| Description: |
Since the early 2000s, gold catalysis has developed particularly well in organic chemistry, offering new highly efficient synthetic methods, generally under very mild conditions. These advances have also led to abundant use in glycoscience, but despite important breakthroughs, the application of gold catalysis in glycochemistry is typically limited to conventional modes of sugar donor activation, in which the gold complex remains strictly confined to the role of a σ- or π-Lewis acid. The research work presented through this manuscript tends to introduce a new paradigm in gold-catalysed glycosylation reactions, by developing catalytic alkynylation reactions in which the gold complex should overcome the intrinsic difficulties of these couplings by contributing to the simultaneous activation of the sugar donor and the alkyne aglycone, based on an original gold/silicon synergistic catalysis strategy. The ideal combination of gold catalyst and counterion was sought (L and X) to achieve optimum catalytic reactivity and stereochemical control both for the alkynylation reaction of simple saturated glycosides and for the alkynylation of glycals. The discovery of a major impact of a hitherto unexploited Au(I) complex counterion in synergistic gold/silicon catalysis associated with a strongly deactivating phosphine has made it possible to extend the field of application of synergistic gold/silicon catalysis beyond the alkynylation of glycosides. ; Depuis le début des années 2000, la catalyse à l'or s'est particulièrement développée en chimie organique, offrant de nouvelles méthodes de synthèse très efficaces, généralement dans des conditions très douces. Ces avancées ont également conduit à une utilisation abondante en glycoscience, mais malgré d'importantes percées, l'application de la catalyse à l'or en glycochimie est typiquement limitée aux modes conventionnels d'activation des donneurs de sucres, dans lesquels le complexe d'or reste strictement confiné au rôle d'un acide σ- ou π-Lewis. Les travaux de recherche ... |
| Document Type: |
doctoral or postdoctoral thesis |
| Language: |
French |
| Relation: |
NNT: 2024NORMLH01 |
| Availability: |
https://theses.hal.science/tel-04887424; https://theses.hal.science/tel-04887424v1/document; https://theses.hal.science/tel-04887424v1/file/PASCARETTI.pdf |
| Rights: |
info:eu-repo/semantics/OpenAccess |
| Accession Number: |
edsbas.12C7DC87 |
| Database: |
BASE |