Syntheses of the methyl 1-deoxy-1-mercapto-D-ribosides and the hydrolysis of methyl 1-deoxy-1-mercapto-α-D-ribopyranoside

Abstract
Syntheses of the four methyl 1-deoxy-1-mercapto-D-ribosides are described. Displacement of the bromine in 2,3,4-tri-O-benzoyl-1-bromo-1-deoxy-β-D-ribopyranose by sodium methanethiolate in dimethylformamide occurs with inversion of configuration without neighbouring group participation. Anomerisation and ring contraction are shown to accompany hydrolysis when methyl 1-deoxy-1-mercapto-α-D-ribopyranoside is treated with hot dilute acid, this is discussed in terms of present theories on glycoside hydrolysis.

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