Recent Progress in the Selective Functionalization of P(O)–OH Bonds

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.