Remote oxidation of unactivated carbon-hydrogen bonds by photoexcited nitrobenzene derivatives is described. The procedure is illustrated by the key step in the conversion of 5α-androstan-3α-ol (3) to 5α-androst-14-en-3-one (6). Introduction of unsaturation into the steroid D ring is accomplished by irradiation of the β-(p-nitrophenyl)propionate ester of 3 (compound 2). As in previously reported remote oxidations utilizing benzophenone derivatives, the selectivity of the reaction is controlled by mutual orientation of the oxidizing agent and the substrate. The advantages and limitations of nitro compounds as reagents for remote oxidation are discussed.