A simple and efficient asymmetric synthesis of 2H-azirine-2-phosphine oxides 3 is described. Thekey step is a solid-phase bound achiral or chiral amine-mediated Neber reaction of β-ketoximetosylates derived from phosphine oxides 1. Reaction of 2H-azirines 3 and 11 with carboxylic acids4 gives phosphorylated ketamides 5 and 12. Ring closure of ketamides 5 and 12 with triphenylphosphine and hexachloroethane in the presence of triethylamine leads to the formation of phosphorylated oxazoles 8 and 13.