This research describes the various Gif-type systems which oxidize selectively saturated hydrocarbons to ketones by non-radical mechanisms. Modifications will enable the selective synthesis of secondary phenylthio-, phenylseleno-, chloro- and bromo-derivatives of saturated hydrocarbons and of secondary polysulfides. In a variation of the GoAggII system (pyridine - acetic acid - ferric chloride + hydrogen peroxide), a system (GoAggIII) has been developed that oxidizes (30% conversion) saturated hydrocarbons to ketones nearly quantitatively. Two intermediates in this system have been characterised which will be studied by physical techniques and by selective trapping. The former are dynamic C-13 NMR, 0-17 NMR, ESCA spectroscopy, Mossbauer spectroscopy and resonance Raman spectroscopy. The Organic Synthesis Program is supporting a continuation of the studies of the complex oxidation system developed by Dr. Barton to selectively functionalize saturated hydrocarbons. The chemistry has parallels in the reactions that are catalyzed by the enzyme methane monooxygenase. This work should lead to a system that can perform this important reaction in a synthetically useful manner.
