alpha-Imino esters are Useful precursors for the synthesis of a variety of types of natural and unnatural alpha-amino acid derivatives, with a wide range of biological activities. Due to the adjacent ester group, alpha-imino esters are more reactive relative to other types of imines and undergo different kinds of reactions, including, organometallics addition, metal catalyzed vinylation and alkynylation, aza-Henry, aza-Morita-Baylis-Hillman, imino-ene, Mannich-type, and cycloaddition reactions, as well as hydrogenation and reduction. This review discusses the mechanism, scope, and applications of the reactions of alpha-imino esters and related compounds in organic synthesis, covering the literature from the last 12 years.