Abstract Studies aimed at the development of new synthetic pathways for the preparation of chiral cyclic oxaza and diaza phosphoramides suitable for use in asymmetric chemistry led us to the investigation of the imide–amide rearrangement of cyclic phosphorimidates. As a result of this work new types of oligomeric organophosphorus compounds, formed by a novel 1, 4-addition type ring opening polymerisation, were identified. These compounds ...