Stereospecific C-Glycosylation by Mizoroki-Heck Reaction A Powerful and Easy-to-Set-Up Synthetic Tool to Access α- and β-Aryl-C-Glycosides

Thibaud Mabit (1, 2) , Aymeric Siard (1) , Frédéric Legros (2) , Stéphane Guillarme (2) , Arnaud Martel (2) , Jacques Lebreton (1) , François Carreaux (3) , Gilles Dujardin (2) , Sylvain Collet (1)

1 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
2 IMMM - Institut des Molécules et Matériaux du Mans
3 ISCR - Institut des Sciences Chimiques de Rennes

A stereospecific Mizoroki-Heck cross-coupling of differently substituted glycals with haloarenes resulting in the exclusive formation of either α- or β-aryl-C-glycosides depending solely on the configuration at C3 was achieved. The reaction was easy to set up because no specific precautions were required concerning moisture or oxygen, and it proceeded by a chirality transfer from C3 to C1. After optimization of cross-coupling conditions, various prepared glycals (7 examples) and arenes (10 examples) were tested, leading stereospecifically to the corresponding aryl-C-glycosides with a carbonyl group at C3, thus opening up new horizons for the total synthesis of glycosylated natural products.

Keywords: β-glycosylation; C-glycosides; Mizoroki-Heck reaction; cross-coupling; α-glycosylation

Domains: Chemical Sciences

Thibaud Mabit, Aymeric Siard, Frédéric Legros, Stéphane Guillarme, Arnaud Martel, et al.. Stereospecific C-Glycosylation by Mizoroki-Heck Reaction A Powerful and Easy-to-Set-Up Synthetic Tool to Access α- and β-Aryl-C-Glycosides. Chemistry - A European Journal, 2018, 24 (53), pp.14069-14074. ⟨10.1002/chem.201803674⟩. ⟨hal-01863769⟩