The Wacker oxidation is a powerful synthetic transformation for converting a terminal olefin into a ketone.
Industrially it is widely used for bulk and fine chemicals, employing molecular oxygen as the oxidant, palladium (II) catalyst and a copper co-catalyst in DMF-water. Thus acetaldehyde is manufactured from ethylene by this process on thousands of tonnes scale in a continuous process.
An alternative approach, which may be more convenient in the laboratory on small scale and in pilot plants where use of oxygen may have safety issues, is to use a peroxide or hydroperoxide to generate a metalloperoxide catalyic species.
A recent review from the group of Matthew Sigman at Utah [Aldrichimica Acta, 2011, 44(3) 55-62] summarises progress in this industrially relevant reaction. Metals such as iridium, ruthenium, platinum, rhodium and palladium have been used with a variety of peroxides and hydroperoxides and sometimes even oxygen itself. It should be remembered that, if scaling up any of these transformations, transition metals do catalyse the decomposition of many peroxo species to oxygen, so there is always an oxygen enriched atmosphere; thus flash points of solvents will be much lower than in air or a nitrogen atmosphere.
Interesting transformations include the conversion of allylic acetates to acetoxyketones and the conversion of a butadiene dimer to acetophenone, shown below.