Sulfamides Direct Radical-Mediated Chlorination of Aliphatic C–H Bonds

Sulfamides guide intermolecular chlorine transfer to gamma-C(sp³) centers. This unusual position-selectivity arises because accessed sulfamidyl radical intermediates engage in otherwise rare 1,6-hydrogen-atom transfer processes. The disclosed chlorine-transfer reaction relies on a light-initiated radical chain-propagation mechanism to oxidize C(sp³)-H bonds.