C–H Nitrooxylation at benzylic positions has been achieved by employing the N- hydroxyphthalimide (NHPI) catalyst/cerium (IV) ammonium nitrate (CAN) reagent system. The nitrooxy groups were demonstrated to function as tentative hydroxy protecting groups, as well as excellent leaving groups for N-and C-substitution reactions. Hence, the present method offers a unique way to synthesize diverse O-, N-, or C-functionalized benzylic ...