Abstract

Phosphorus Fluoride Exchange (PFEx) is a new click chemistry technology that hinges on the creation of innovative hubs to unlock its potential and broaden its applications. In this study, we outline some guiding principles for PFEx hub development and validate these principles by developing a new hub, 2‐substituted‐alkynyl‐1‐cyclotriphosphazenes (SACPs). These SACPs serve as versatile PFEx hubs with stable functionality and orthogonal reactivity, exemplifying their utility within the Diversity Oriented Clicking (DOC) framework. We demonstrate that SACPs interact with various 1,3‐dipoles, enabling the synthesis of phosphorus‐rich compounds through sequential cycloaddition and PFEx reactions, thus pioneering new synthetic routes for wide application of click chemistry.