The catalytic and enantioselective hydrophosphonylation of cyclic imines is described for the first time. In addition, we have uncovered a new and highly efficient asymmetric approach to cyclic cc-amino phosphonates using thiazolines as the imine model component. The desired pharmaceutically interesting phosphonates 5a-e could be synthesized by a heterobimetallic (R)-LnPB-catalyzed (Ln = lanthanoid metal, P = potassium, B = (R)=binaphthol) hydrophosphonylation of the C=N double bond with up to 98% enantiomeric excess and up to 98% chemical yield. Using other types of organometallic catalysts (titanium-(IV) complexes), the reaction proceeds with modest enantioselectivity. A detailed investigation concerning the dependence of enantioselectivity and chemical yield, respectively, on a series of reaction parameters (e.g.; lanthanoid and alkali metal, solvent, reaction temperature, pressure, and catalytic amount) is reported. An optimized catalytic lanthanoid system "(R)-YbPB (5 mol %)/50 degrees C/48 h/THF-toluene (1:7)" was found. The catalytically active complex was isolated and analyzed by spectroscopic methods. In addition, P-31 and H-1 NMR spectroscopic and LDI-TOF mass spectrometric investigations were carried out to support a postulated mechanistic course for this (R)-LnPB-complex-catalyzed hydrophosphonylation reaction.