Intramolecular oxygen transfer from nitro groups to CC bonds mediated by iridium hydrides

The functionalized alkynes o-RC equivalent to C(C6H4)NO2 (R = H or alkyl) formally insert into two iridium hydrides, during which O-transfer of the nitro group into the C equivalent to C bond of o-RC equivalent to C(C6H4)NO2 is observed. For the terminal alkyne with R = H, iridium(III) nitroso complexes were isolated. For internal alkynes with R = Me or Pr-n, iridium hydride anthranil complexes were obtained as a result of O-transfer with a different regiochemistry. Mechanisms for these transformations, including a previously unknown O-transfer step from the nitro to the RC equivalent to C bond, are proposed.