PhI(OAc)2-Promoted Site-Selective C–H Chlorination of (Hetero)arenes with p-Toluenesulfonyl Chloride

An efficient and practical system for metal-free catalytic chlorination of (hetero)arenes by using readily available and inexpensive TsCl and PhI(OAc)₂ is described. This newly developed protocol has been achieved by the nonsymmetric iodane generated by a combination of PhI(OAc)₂ and TsCl. The broad substrate scope, good functional group tolerance, excellent regioselectivity, and short reaction times make this method attractive for the late-stage chlorination of complex drug-like scaffolds.