Substitution of the Participating Group of Glycosyl Donors by a Halogen Atom: Influence on the Rearrangement of Transient Orthoesters Formed during Glycosylation Reactions

Antoine Joosten (1) , Mélissa Boultadakis-Arapinis (2, 3, 4) , V. Gandon (5, 6) , L. Micouin (2, 3, 4) , Thomas Lecourt (1)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse
2 UPD5 - Université Paris Descartes - Paris 5
3 USPC - Université Sorbonne Paris Cité
4 LCBPT - UMR 8601 - Laboratoire de Chimie et de Biochimie Pharmacologiques et Toxicologiques
5 ICSN - Institut de Chimie des Substances Naturelles
6 ICMMO - Institut de Chimie Moléculaire et des Matériaux d'Orsay

Substitution of the participating group of glycosyl donors by a halogen atom is shown to specifically induce degradation of transient orthoesters formed during glycosylation reactions, depending on the nature of the acceptor, and to affect the protonation profile of those intermediates. Following these findings, bromo- and chloroacetates, which are major protecting groups in glycochemistry because they are orthogonal to other esters, should be considered with care as participating groups in the future.

Domains: Chemical Sciences

Antoine Joosten, Mélissa Boultadakis-Arapinis, V. Gandon, L. Micouin, Thomas Lecourt. Substitution of the Participating Group of Glycosyl Donors by a Halogen Atom: Influence on the Rearrangement of Transient Orthoesters Formed during Glycosylation Reactions. Journal of Organic Chemistry, 2017, 82 (6), pp.3291-3297. ⟨10.1021/acs.joc.6b03088⟩. ⟨hal-02046285⟩