Chiral phosphonate esters have been widely applied in the fields of organic chemistry, medicine, and photoelectric materials. However, it requires the challenging enantioselective synthesis of cyclic phosphonate esters with the desired chiral configuration. The two epimers of 2-oxo-2H-1,3,2-dioxaphosphorinane derivatives should have different reactivities in Pd-catalyzed coupling reactions, which could lead to an effective methodology for the asymmetric synthesis of 2-oxo-2-aryl-1,3,2-dioxaphosphorinane derivatives. A thorough investigation of the coupling reactions both computationally and experimentally led to the stereoselective synthesis of chiral cyclic phosphonate esters. The axial isomer of products can be obtained with both high diastereoselectivity and good chemical yields from the mixture of 2-oxo-2H-1,3,2-dioxaphosphorinane derivatives under kinetically controlled conditions.