Primary and secondary alcohols react with vinyl or isopropenyl acetate at room temperature in the presence of catalytic amounts (0.05−1 mol %) of Y5(OiPr)13O to give the corresponding esters. In selected cases, the yttrium catalyst promotes the selective O-acylation of amino alcohols without the formation of the amide. Enol esters also react with α-amino acid esters in the absence of a catalyst, at room temperature, to give the corresponding amides.