In situ Generation of Hypervalent Iodine Reagents for the Electrophilic Chlorination of Arenes

Efficient metal‐free methods for the electrophilic chlorination of arenes using PIFA and simple chlorine sources are reported. The in situ formation of PhI(Cl)OCOCF 3 from PIFA and KCl is proposed, which resulted in a chlorinating species for moderately activated arenes. Moreover, the in situ formation of PhICl 2 from PIFA and TMSCl resulted in an excellent approach for the chlorination of a great variety of arenes (20 examples) in high yields, even when working on a multigram scale.