title: Preparation of 1-C-glycosyl aldehydes by reductive hydrolysis.
abstract: Reductive hydrolysis of various protected glycosyl cyanides was carried out using DIBAL-H to form aldimine alane intermediates which were then hydrolyzed under mildly acidic condition to provide the corresponding aldehyde derivatives. While 1-C-formyl glycal and 2-deoxy glycosyl derivatives were stable during isolation and storage 1-C-glycosyl formaldehydes in the gluco, galacto and manno series were sensitive and decomposition occurred by 2-alkyloxy elimination. A one-pot method using N,N'-diphenylethylenediamine to trap these aldehydes in stable form was developed. Reductive hydrolysis of glycosyl cyanides offers valuable aldehyde building blocks in a convenient way which can be applied in the synthesis of complex C-glycosides.
authors.affiliation: Institute of Biomolecular Chemistry, Chemical Research Center, Hungarian Academy of Sciences, PO Box 17, 1525 Budapest, Hungary.
authors.forename: Szabolcs
authors.initials: S
authors.lastname: Sipos
authors.forename: István
authors.initials: I
authors.lastname: Jablonkai
mesh_terms: D000447:Aldehydes / Q000138:chemical synthesis*; D001688:Biological Products / Q000138:chemical synthesis*; D032701:Biomimetics / Q000379:methods*; D002850:Chromatography, Gel; D003486:Cyanides / Q000737:chemistry; D005029:Ethylenediamines / Q000737:chemistry*; D006027:Glycosides / Q000138:chemical synthesis*; D006868:Hydrolysis; D009682:Magnetic Resonance Spectroscopy; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D001688:Biological Products; D003486:Cyanides; D005029:Ethylenediamines; D006027:Glycosides; C518332:diphenylethylenediamine