AbstractThe asymmetric reaction of the chiron 2(5H)‐furanones (4a–4c) with the Horner‐Emmons reagents (5a—5b) has been investigated. The newly chiral organophosphorus derivatives 6 and 7 were obtained using the phosphoryl‐stabilized carbanion as a building block in DMSO under mild conditions. Through the asymmetric introduction, the Horner‐Emmons reagent could be transformed to a chiral building block to afford the novel functionalized phosphorus derivatives. The structures of the synthesized compounds 6 and 7 were identified on the basis of their elementary and spectroscopic data, such as IR, 1H NMR, 13C NMR, MS and X‐ray crystallography. These results provided a valuable approach to the synthesis of potentially interesting chiral organophosphorus derivatives and probing their biological activities.