Metal-catalyzed functionalisations


Access to unnatural glycosides by metal-catalyzed functionalisation of glycal substrates

Development of new access to glycoconjugates has become of great interest in synthetic chemistry. In particular, glycoconjugates possessing an unnatural bond are largely studied due to their enzymatic and chemical stabilities towards C-O and C-N natural links.
Our expertise deals with the metal-catalyzed functionalisation of glycal substrates using two different reactivities:
- Cross-coupling reactions on 2-iodoglycal starting compounds for the formation of C-C, C-N or C-P bonds : palladium-catalyzed aminocarbonylation (A), carbonylative Suzuki-Miyaura reaction (C), cyanation in aqueous media (D) dual nickel/copper-catalyzed amidation (E) and palladium-catalyzed phosphonylation (F).
- Directed C-H functionalisation reactions of the pseudo-anomeric position of C2-amidoglycals: palladium-catalyzed C-H arylation and nickel-catalyzed C-H alkenylation (B).

Selected publications

1. “CO” as a Carbon Bridge to Build Complex C2-Branched Glycosides Using a Palladium-Catalyzed Carbonylative Suzuki–Miyaura Reaction from 2-Iodoglycals. de Robichon, M.; Bordessa, A.; Lubin-Germain, N.; Ferry, A. J. Org. Chem. 2019, 84, 3328-3339.

2. Access to C-aryl/alkenylglycosides by directed Pd-catalyzed C–H functionalisation of the anomeric position in glycal-type substrates. de Robichon, M.; Bordessa, A.; Malinowski, M.; Uziel, J.; Lubin-Germain, N.; Ferry, AChem. Commun. 201955, 11806-11808.

3.  Mild Palladium‐Catalyzed Cyanation of Unprotected 2‐Iodoglycals in Aqueous Media as Versatile Tool to Access Diverse C2‐Glycoanalogues. Malinowski, M.; Tran, T. V.; de Robichon, M.; Lubin-Germain, N.; Ferry, A. Adv. Synth. Catal. 2020362, 1184-1189.

4. Glycosamine Derivatives through Metal-Catalyzed C−N Bond Formation on Protected and Unprotected 2-Iodoglycals. Malinowski, M.; Banoun, C.; de Robichon, M.; Lubin-Germain, N.; Ferry, A. Eur. J. Org. Chem. 2021, 1521–1524

5. Directed Nickel-Catalyzed Pseudo-Anomeric C−H Alkynylation of Glycals as an Approach towards C-Glycoconjugate Synthesis. de Robichon, M.; Branquet, D.; Uziel, J.; Lubin-Germain, N.; Ferry, A.  Adv. Synth. Catal. 2021,363 (22), pp. 5138-5148