Cu-Catalyzed Site-Selective Benzylic Chlorination Enabling Net C–H Coupling with Oxidatively Sensitive Nucleophiles

Site-selective chlorination of benzylic C–H bonds is achieved using a Cu I Cl/bis(oxazoline) catalyst with N -fluorobenzenesulfonimide as the oxidant and KCl as a chloride source. This method exhibits higher benzylic selectivity, relative to established chlorination protocols, and is compatible with diverse alkyl arenes. Sequential benzylic C–H chlorination/nucleophilic substitution affords C–O, C–S, and C–N coupling products with oxidatively sensitive coupling partners.