Substitution of the Participating Group of Glycosyl Donors by a Halogen Atom: Influence on the Rearrangement of Transient Orthoesters Formed during Glycosylation Reactions.
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.
Normandie Univ , INSA Rouen, UNIROUEN, CNRS, COBRA UMR 6014, 76000 Rouen, France.
Antoine
A
Joosten
Université Paris Descartes , Sorbonne Paris Cité, CNRS (UMR 8601), 75006 Paris, France.
Mélissa
M
Boultadakis-Arapinis
Institut de Chimie Moléculaire et des Matériaux d'Orsay, CNRS UMR 8182, Univ. Paris-Sud, Université Paris-Saclay , Bâtiment 420, 91405 Orsay, France.
Vincent
V
Gandon
Université Paris Descartes , Sorbonne Paris Cité, CNRS (UMR 8601), 75006 Paris, France.
Laurent
L
Micouin
Normandie Univ , INSA Rouen, UNIROUEN, CNRS, COBRA UMR 6014, 76000 Rouen, France.
Thomas
0000-0002-2532-3012
T
Lecourt