Synthesis of N-unsubstituted, mono- and disubstituted carbohydrate-1- O-carbamates and their behaviour in glycoside syntheses

Abstract

The syntheses of 44 1-carbamates from six different 1- O-unprotected carbohydrate derivatives (compounds 1– 6), representing typical protecting pattern in glycoside synthesis, are described. The carbamate function is N-unsubstituted (compounds 1b– 6b), mono- (compounds a: N-trichloroacetyl, c: N-monochloroacetyl, d: N-acetyl, e: N-ethyl, f: N-allyl, g: N-phenyl) or disubstituted (compounds h: imidazolyl, i: N-diethyl, j: N-diphenyl). Additionally, three N-chlorosulfonyl carbamates are synthesized and used as intermediates for the synthesis of N-unsubstituted compounds b. The accessibility of these compounds is described and compared. Some of the carbamates ( 1, 4, 5a– j) are used as model compounds for systematic investigations in glycoside syntheses. Selected experimental data (reaction conditions, anomeric ratios, rotation values, selected NMR data) are tabulated.