A new glycosidation method through nitrite displacement on substituted nitrobenzenes.
Benzyl, benzoyl, and acetyl protected 1-OH and 1-SH glycoses in the glucose, glucosamine, galactose, mannose, and lactose series react with nitrobenzenes activated by one or two electron withdrawing substituents like nitro and cyano to afford the corresponding aryl glycosides in 50-100% yield. The S(N)Ar displacement of nitrite by 1-OH glycoses is reversible and gives predominantly the alpha-glycosides, whereas 1-SH glycoses do not anomerize and afford the beta-glycosides. Thus, the prepared dicyanophenyl gycosides are useful building blocks for the preparation of phthalocyanine-glycoconjugates via template synthesis.
Alvarez-Micó
Xavier
X
Institute of Organic Chemistry, University of Tuebingen, Auf der Morgenstelle 18, 72076 Tuebingen, Germany.
Calvete
Mario J F
MJ
Hanack
Michael
M
Ziegler
Thomas
T
D006027:Glycosides / Q000138:chemical synthesis*; D006031:Glycosylation; D007211:Indoles / Q000737:chemistry; D054833:Isoindoles; D009573:Nitrites / Q000737:chemistry*; D009578:Nitrobenzenes / Q000737:chemistry*
D006027:Glycosides; D007211:Indoles; D054833:Isoindoles; D009573:Nitrites; D009578:Nitrobenzenes; C013647:phthalocyanine