A Three-Phase Four-Component Coupling Reaction: Selective Synthesis of o-Chloro Benzoates by KCl, Arynes, CO2, and Chloroalkanes.

A transition-metal-free three-phase four-component coupling reaction (3P-4CR) involving KCl, arynes, chloroalkanes and CO2 has been reported for the first time, enabling the incorporation of both chloro and CO2 into an aryne simultaneously. The reactions for the synthesis of different types of o-chloro benzoates can be selectively modulated by the chloroalkane utilized. The corresponding products can be alternatively transformed for postsynthetic functionalizations conveniently.