A series of Cp*Ir complexes are active precatalysts in C-H oxidation of cis-decalin, cyclooctane, 1-acetyl-pyrrolidine, tetrahydrofurans, and gamma-lactones. Moderate to high yields were achieved, and surprisingly, high selectivity for mono-oxidation of cyclooctane to cyclooctanone was observed. Kinetic isotope effect experiments in the C-H oxidation of ethylbenezene to acetophenone yield k(H)/k(D) = 15.4 +/- 0.8 at 23 degrees C and 17.8 +/- 1.2 at 0 degrees C, which are consistent with C H oxidation being the rate-limiting step with a significant tunneling contribution. The nature of the active species was investigated by TEM, UV-vis; microfiltration, and control experiments. DFT calculations showed that the C-H oxidation of cis-decalin by Cp*Ir(ppy)(Cl) (ppy = o-phertylpyridine) follows a direct oxygen insertion mechanism on the singlet potential energy surface, rather than the radical rebound route that would be seen for the triplet, in good agreement with the retention of stereochemistry observed in this reaction.