Rapid Synthesis of Zwitterionic Phosphonium Benzoates by a Three‐Component Coupling Involving Phosphines, Arynes and CO2

A mild and easy to perform multicomponent coupling involving phosphines, arynes generated from 2-(trimethylsilyl)aryl triflates, and CO2 allowing the transition-metal-free synthesis of zwitterionic phosphonium benzoates has been developed. The reaction proceeds via the generation of 1 : 1 zwitterionic intermediates from phosphines and arynes followed by the interception with CO2 to deliver the carboxylates in moderate to good yields instead of the anticipated benzooxaphosphol-3(1H)-ones.