Robust perfluorophenylboronic acid-catalyzed stereoselective synthesis of 2,3-unsaturated O-, C-, N- and S-linked glycosides

Abstract

A convenient protocol was developed for the synthesis of 2,3-unsaturated C-, O-, N- and S-linked glycosides (enosides) using 20 mol % perflurophenylboronic acid catalyst via Ferrier rearrangement. Using this protocol, D-glucals and L-rhamnals reacted with various C-, O-, N- and S-nucleophiles to give a wide range of glycosides in up to 98% yields with mainly α-anomeric selectivity. The perflurophenylboronic acid successfully catalyzed a wide range of substrates (both glucals and nucleophiles) under very mild reaction conditions.

Relevant Advances in the Synthesis and Applications of N‐Glycopyranosides

“…The methodology consisted in reacted D‐glucals and L‐rhamnals with various N ‐acceptor to provide several N ‐glycosides in up to 72 % yields and high α‐anomeric stereoselectivity (Scheme 8). [23] On the other hand, perfluorophenylboronic acid successfully catalyzed several glucals and N ‐nucleophiles under very mild reaction conditions.…”

“…However, other Lewis acids such as HBF 4 •SiO 2 , [17] Cu(OTf) 2 , [18] FeCl 3 , [18] FeCl 2 , [18] Sn(OTf) 2, [18,19] Yb(OTf) 2 , [18] PtCl 2, [18] IrCl 3 , [18] RuCl 3, [18,19] ZnCl 2, [18] ZnCl 2 /Al2O 3 , [18] Gd(OAc) 3 .6H 2 O, [20] GdBr 3 .xH 2 O [21] GdB 6 , [20] Gd(NO 3 ) 3 , [20] Gd(OTf) 3 , [20] Hf(OTf) 4 , [20] Pd-(TFA) 2 , [22] Pd(Ph 3 P)A 2 Cl 2 , [22] Pd(PhCN) 2 Cl 2 , [22] Pd(OAc) 2 , [22] Pd 2 (dba) 2 , [22] perfluorophenylboronic acid, [23] (Pd 2 (dba) 3 , [24] and Pd(PPh 3 ) 4 , [24] have been reported for synthesis of N-glycosides.…”

Occurrence, Biosynthesis, Synthesis and Applications Of S-Glycosides: an Overview

“…Outras reações de síntese para obtenção de S-glicosídeos 2,3-insaturados são utilizando a metodologia de Ferrier a glicais são descritos na literatura. [108][109][110][111][112][113][114][115][116][117][118][119][120]…”

Iridium-promoted deoxyglycoside synthesis: stereoselectivity and mechanistic insight

“…2 However, glycosylation by these approaches is often conducted at either low or high temperatures, with the possibility of obtaining appreciable amounts of unwanted hemiacetal side products. 2 b , c , e ,3 In comparison, transition metal catalyzed glycosylation with glycals, compatible with acid and base-labile substrates and amenable to moderate conditions, promises improved alternatives to the conventional methods. During recent years, transition metals have played an important role in the chemical synthesis of oligosaccharides, with a flow of intriguing glycosylation methodologies involving a variety of transition metal catalysts reported.…”