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The synthesis of α,β-dehydro-α-aminophosphonic and α,β-dehydro-α-aminophosphinic acid derivatives is discussed. The most important synthetic pathways to the above-mentioned compounds have been divided into four groups depending on the type of bond formed as the last one. The configuration at the C=C double bond can be established based on the specific coupling constants 3JHP and 3JCP for the appropriate Z- and E-stereoisomers. The application of α,β-dehydro-α-aminophosphonates and α,β-dehydro-α- aminophosphinates, particularly in the enantioselective catalytic hydrogenation, is also discussed.