A new highly selective synthesis of amides and carbamates is described. In both cases the syntheses involve the formation of carbonyl imidazole intermediates which subsequently undergo previously unreported selective reactions with primary amines. Acid imidazolides with sufficient chain length will exclusively react with primary amines even in the presence of secondary and tertiary functionality. The imidazole carboxylic esters of secondary or tertiary alcohols also react selectively with primary amines, forming controlled carbamate structures.
A new highly selective synthesis of dialkyl carbonates is described. The procedures rely on the previously unknown selectivity of imidazole carboxylic esters synthesized by the reaction of 1,1′-carbonyldiimidazole with alcohols. The imidazole carboxylic esters of secondary or tertiary alcohols form carbonates through the exclusive reaction with primary alcohols in polyols containing mixtures of primary, secondary, and tertiary hydroxyl groups without the need for protection. Controlled cyclic carbonate formation is also described.
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