As we all know, organic phosphorus compounds have high application values in chemical industries. Compared with traditional compounds with P–X (X = Cl, Br, I) and P–H bonds, phosphorylation reagents containing P(O)–OH bonds are stable, environmentally friendly, and inexpensive. However, in recent years, there have been few studies on the selective functionalization of P(O)–OH bonds for the fabrication of P–C and P–Z bonds. In general, four-coordinated P(O)–OH compounds have reached coordination saturation due to the phosphorus atom center, but cannot evolve the phosphorus coordination center through intra-molecular tautomerization; however, the weak coordination effects between the P=O bond and transition metals can be utilized to activate P(O)–OH bonds. This review highlights the most important recent contributions toward the selective functionalization of P(O)–OH bonds via cyclization/cross coupling/esterification reactions using transition metals or small organic molecules as the catalyst.

众所周知，有机磷化合物在化学工业中具有很高的应用价值。与具有P–X（X = Cl，Br，I）和P–H键的传统化合物相比，含有P（O）–OH键的磷酸化试剂稳定，环保且廉价。但是，近年来，很少有人研究制造P–C和P–Z键的P（O）–OH键的选择性功能化。通常，由于磷原子中心，四配位的P（O）-OH化合物已经达到配位饱和，但是不能通过分子内互变异构作用释放出磷配位中心。但是，P = O键和过渡金属之间的弱配位作用可以用来激活P（O）-OH键。