Cyclohexane acetoxylation

The chief problem with these systems from the synthetic point of view is the relatively nq)id oxidation of the catalyst Traylor et al. have introduced tetraphenylpoiphyrins bearing chloro substituents at the ortho positions, which make the system much more robust, and 440 turnovers have been observed with cyclohexane, for example. Unfortunately, these catalysts are not yet cottunercially available. A metal-catalyzed acetoxylation of cyclohexane has been reported which utilizes Et3NOfiton(II)/CI C02H. ... 

Acetoxylation. ct. S-Unsaturated ketones can be or -acetyloxy-lated with Mn(OAc)3. Lower yields are usually due to dimerization of the carbonyl radical. Recently, an improved protocol was developed, using a mixture of acetic acid/benzene as solvent, drastically improving the yield and lowering reaction times (eq 45). Acetonitrile and cyclohexane can also replace benzene as the solvent and only 1.25 equiv of Mn(OAc)3 is needed for a complete conversion. The method is compatible with a -substituted substrates, giving access to tertiary alcohols (eq 46). The increase in steric hindrance does, however, tend to decrease the acetoxylation yield. 

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