Introduction of benzylidene group at α-position of enamines derived from cyclic ketones substantially increases strength of C-P bond thus permitting further syntheses without splitting of the C-P bond. A wide set of phosphorylated derivatives of type (I) were prepared and their properties were studied. Combination of an enamine moiety with other nucleophilic centers such as C or N in a molecule allows to carry out cyclisation giving five- and six-membered phosphorus-containing heterocycles of types (II, III).