Abstract Cycloalkylphosphonates 2 of different sizes (from cyclopropyl to cycloheptyl) bearing various functional groups Z in a position were synthesized by bis-alkylation of α- functional methylphosphonates 1 and Ω-dibromoalkanes in presence of base. The choice of the basic system is determined by the nature of Z. With powerful electron-withdrawing groups, NaH-THF/DMSO (Method A, for Z= CN, SO2R) or liquid-solid phase transfer ...