摘要：

A review is Given on oxidation of terminal olefins to methyl ketones by O2,ROOH, or H2O2 in the presence of rhodium, palladium, platinum and iridium catalysts. a) Rhodium catalysts can use both oxygen atoms of the dioxygen molecule for the oxidation of two moles of terminal olefins by the coupling of a cyclic or pseudocyclic peroxymetalation process with a Wacker-type intramolecular hydroxymetalation pathway. b) Palladium catalysts act as alkyl peroxidic (stable) or hydroperoxidic (generated from H2O2 or protonation of peroxo complexes) reactive species for the oxidation of terminal olefins to methyl ketones, c) Platinum peroxo or hydroperoxidic species are generally inactive, but a stable and reactive platinum tert-butyl peroxide trifluoroacetate complex has been synthesized. d) Although iridium catalysts can coordinate both O2 and olefin on the same metal center, they exhibit a different behavior with respect to rhodium complexes, and are generally poor oxidation catalysts. However IrOOH species, generated from reaction of O2 with iridium hydride was found to oxidize coordinated cyclooctene to cyclooctanone. The problem of activation and transfer of molecular oxygen by the stepwise utilization of both oxygen atoms will be discussed.

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