KO t Bu‐Catalyzed Construction of Fully Substituted Phosphate Ester‐Functionalized 5‐Thioureido‐Triazoles

A transition‐metal‐free KO t Bu‐catalyzed three‐component reaction has been established, involving various nitriles, azides, and phosphoroisothiocyanatidates, enabling the construction of fully substituted phosphate ester‐functionalized 5‐thioureido‐triazoles. In this process, nitriles undergo cycloaddition with azides in the presence of a base and the resulting triazolamine and triazole nitrogen anion intermediates subsequently captured by the phosphoroisothiocyanatidate. This protocol is characterized by being transition‐metal‐free, a broad substrate scope, high regioselectivity, and compatibility with late‐stage functionalization.