The octahedral geometry of pentavalent hexacoordinated phosphorus allows the formation of chiral anions by complexation of the central phosphorus atom with three bidentate ligands. These simple-to-make derivatives can be combined with chiral cations and often display efficient NMR chiral shift, resolving and asymmetry-inducing properties. This paper is a short review of our research efforts directed towards the development of chiral anion mediated asymmetric chemistry.