Functionalization of Saturated Hydrocarbons. 14. Further Studies on the Mechanism of Gif-Type Systems

Article abstract of DOI:10.1021/ja00200a037

The photolysis (W light) of acyl derivatives of N-hydroxy-2-thiopyridone in pyridine-acetic acid permits a study of the partioning of secondary radicals between oxygen, pyridine, and the thione function.Comparison with the Gif^IV oxidation system for saturated hydrocarbons confirms that radicals are not involved in oxidation at secondary positions.On the contrary, radical behavior at the tertiary position in adamantane is again established.The two recently introduced Gif-type systems, GoAgg^I and GoAgg^II, have been shown to give the same overall selectivity in attack on adamantane with the usual coupling of the tertiary radical with pyridine.