PhI(OAc)<sub>2</sub>‑Promoted Site-Selective\nC–H Chlorination of (Hetero)arenes with <i>p</i>‑Toluenesulfonyl\nChloride

An\nefficient and practical system for metal-free catalytic chlorination\nof (hetero)arenes by using readily available and inexpensive TsCl\nand PhI(OAc)<sub>2</sub> is described. This newly developed protocol\nhas been achieved by the nonsymmetric iodane generated by a combination\nof PhI(OAc)<sub>2</sub> and TsCl. The broad substrate scope, good\nfunctional group tolerance, excellent regioselectivity, and short\nreaction times make this method attractive for the late-stage chlorination\nof complex drug-like scaffolds.