Reductive cleavage of the positional isomers of benzoylated and methylated methyl alpha-D-mannopyranoside.
The four O-benzoyl-tri-O-methyl positional isomers, the six di-O-benzoyl-di-O-methyl positional isomers, the four tri-O-benzoyl-O-methyl positional isomers, and the tetra-O-benzoyl derivative of methyl alpha-D-mannopyranoside were synthesized, characterized, and subjected to reductive cleavage in the presence of triethylsilane and trimethylsilyl trifluoromethanesulfonate. The reactions were monitored by 1H NMR spectroscopy in order to establish the rates of the reactions and the identities of the products so formed. The tetra-O-benzoyl derivative, all tri-O-benzoyl-O-methyl positional isomers, and the 2.4-di-O-benzoyl-3.6-di-O-methyl positional isomer were fully stable to reductive-cleavage conditions, but the other di-O-benzoyl-di-O-methyl positional isomers and all O-benzoyl-tri-O-methyl positional isomers were converted to their respective 1.5-anhydro-D-mannitol derivatives via reductive cleavage of their anomeric carbon-oxygen bonds. For the mono-O-benzoyl positional isomers, the rate of reductive cleavage decreased in the order 2-O-benzoyl > 6-O-benzoyl > 3-O-benzoyl approximately 4-O-benzoyl. Moreover, all mono-O-benzoyl positional isomers were cleaved at a much faster rate than the di-O-benzoyl positional isomers. These results suggest that both anchimeric assistance and inductive effects of the ester groups contribute to the observed reaction rate. Based upon these results it is suggested that reductive cleavage of benzoylated polysaccharides might serve as a means to cleave selectively at branched residues.
Rozanas
C R
CR
Department of Chemistry, University of Minnesota, Minneapolis 55455, USA.
Gray
G R
GR
D001565:Benzoates / Q000737:chemistry*; D019817:Benzoic Acid; D002851:Chromatography, High Pressure Liquid; D007700:Kinetics; D008745:Methylation; D008766:Methylmannosides / Q000737:chemistry*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D013237:Stereoisomerism
D001565:Benzoates; D008766:Methylmannosides; C008466:methylmannoside; D019817:Benzoic Acid