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.