Aryne‐derived phosphonium zwitterions as a divergent platform for organophosphorus synthesis

Abstract Aryne‐based three‐component coupling reactions provide a powerful strategy for constructing two vicinal bonds on an aromatic ring in a single operation. In this Personal Account, we summarize our group's efforts to explore this strategy for organophosphorus synthesis using phosphites as nucleophilic partners. Nucleophilic addition of a phosphite to an aryne, generated in situ from an ortho ‐silylaryl triflate upon fluoride activation, affords an ortho ‐phosphonium aryl anion—a 1,3‐zwitterionic intermediate that combines a nucleophilic carbon and an electrophilic phosphonium center within one molecule. This dual reactivity underlies the divergent transformations developed in our laboratory. We discuss the reaction design, substrate scope, mechanistic rationale, and synthetic utility of these transformations, highlighting how a common zwitterionic intermediate can be steered toward structurally distinct organophosphorus frameworks.