Silver-Catalyzed C(sp³)–H Chlorination

A silver-catalyzed chlorination of benzylic, tertiary, and secondary C­(sp³)–H bonds was developed. The reaction proceeded with as low as 0.2 mol % catalyst loading at room temperature under air atmosphere with synthetically useful functional group compatibility. The regioselectivity and reactivity tendencies suggest that the chlorination proceeded through a radical pathway, but an intermediate alkylsilver species cannot be ruled out.