The diastereomerically pure organophosphorus derivatives containing multiple chiral centers 5 and 5 were obtained, respectively, in 62%-84% yields with ≥98% de (diastereomeric excess) via asymmetric reaction of the chiron, 3-bromo-2(5H)-furanone 4 with racemic diethyl a-hydroxyl- substituted-phosphonates 3 + 3 and further through the separation of the diastereomeric mixture by chromatography. The structures of the chiral organophosphorus derivatives were identified on the basis of their elementary and spectro-scopic data, such as IR, 1H NMR, 13C NMR, MS and X-ray crystallography. In this report, the synthetic methods of the active organophosphorus substrates, the structure charac-terization and resolution, the optical purity and the stereo-chemistry of the chiral products were discussed. These re-sults provide a new idea and a good method for synthesizing some natural organophosphorus compounds and approach-ing their biological activities, also a facile route to the appli-cation of organophosphorus substrates. The diastereomerically pure organophosphorus derivatives containing multiple chiral centers 5 and 5 were obtained, respectively, in 62-84% yields with ≥ 98% de (diastereomeric excess) via asymmetric reaction of the chiron, 3-bromo-2 (5H) 4 with racemic diethyl a-hydroxyl-substituted-phosphonates 3 + 3 and further through the separation of the diastereomeric mixture by chromatography. The structures of the chiral organophosphorus derivatives were on the basis of their elementary and spectro-scopic data, such as IR , 1H NMR, 13C NMR, MS and X-ray crystallography. In this report, the synthetic methods of the active organophosphorus substrates, the structure charac-terization and resolution, the optical purity and the stereo-chemistry of the chiral products were discussed. These re-sults provide a new idea and a good method for synthesizing some natural organophosphorus compounds and approach-ing their biological activities, also a facile route to the appli-cation of o rganophosphorus substrates.