THE SELECTIVE FUNCTIONALIZATION OF SATURATED-HYDROCARBONS .27. A NEW MICHAEL-TYPE ADDITION-REACTION FOR SATURATED-HYDROCARBONS NOT INVOLVING RADICAL CHEMISTRY

The oxidation of saturated hydrocarbons with Fe(III)-tert-butyl hydrop eroxide (TBHP) under Gif conditions in the presence of methyl vinyl ke tone (MVK) affords adducts (a Michael type reaction) in which the hydr ocarbon has been added to the MVK and a tert-butylperoxy group has bee n inserted a- to the carbonyl group. The adducts slowly eliminate tert -butanol to give alpha-diketones. Extensive competitive trapping exper iments with TEMPO have shown that in all reactions with carbon radical s TEMPO traps very efficiently as expected. TEMPO is, however, an inef ficient trap for the iron-carbon bond (Intermediate A) postulated as t he basis of the extensive Gif chemistry of saturated hydrocarbon.