•Green catalytic oxidations of alcohols with dioxygen and hydrogen peroxide in water.•Tungsten, molybdenum and vanadium catalysts for oxidations with hydrogen peroxide.•Palladium(II) diamine ...complexes and supported palladium nanoparticles as catalysts.•Stable N-oxy radicals as organocatalysts for the aerobic oxidation of alcohols.•Biocatalytic aerobic oxidations mediated by laccase/TEMPO.
Catalytic oxidations of alcohols, with dioxygen or hydrogen peroxide as the primary oxidant, in aqueous reaction media are reviewed. Selective alcohol oxidations with hydrogen peroxide generally involve early transition elements, mostly tungsten, molybdenum and vanadium, in high oxidation states and peroxometal complexes as the active oxidants. Aerobic oxidations, in contrast, involve oxidative dehydrogenation, usually catalyzed by late transition elements, e.g. water soluble palladium(II)-diamine complexes, or supported nanoparticles of Pd or Au as hybrid species at the interface of homogeneous and heterogeneous catalysis. Alternatively, water soluble organocatalysts, exemplified by stable N-oxy radicals such as TEMPO and derivatives thereof, in conjunction with copper catalysts, are efficient catalysts for the aerobic oxidation of alcohols. Metal-free variants of these systems, e.g. employing nitrite or nitric acid as a cocatalyst, are also effective catalysts for aerobic alcohol oxidations. Finally, enzymatic aerobic oxidations of alcohols employing oxidases as catalysts are described. In particular, the laccase/TEMPO system is receiving much attention because of possible applications in the selective oxidations of diols and carbohydrates derived from renewable resources.
Correction for '
In situ
spectroscopic investigations of MoO
x
/Fe
2
O
3
catalysts for the selective oxidation of methanol' by Catherine Brookes
et al., Catal. Sci. Technol.
, 2016,
6
, 722-730.
The use of Oxone and a palladium(II) catalyst enables the efficient allylic CH oxidation of sterically hindered alpha-quaternary lactams which are unreactive under known conditions for similar ...transformations. This simple, safe, and effective system for CH activation allows for unusual tunable selectivity between a two-electron oxidation to the allylic acetates and a four-electron oxidation to the corresponding enals, with the dominant product depending on the presence or absence of water. The versatile synthetic utility of both the allylic acetate and enal products accessible through this methodology is also demonstrated.
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