1.3- Dicarbonyl compounds oxidations, manganese acetate

The low yield in this reaction might be caused by a number of reasons. First, the overall reaction is only rapid for readily enolizable compounds. 1,3-Dicarbonyl compounds will therefore be a better choice as compared to acetic acid. Second, to prevent oxidation of radical 54, it is advantageous to work with excess diene and therefore speed up trapping of 54 through diene addition. Finally, lactone 55 can, as an enolizable compound itself, also be oxidized by manganese(III) acetate and form various oxidation products. Shorter reaction time and the use of understoichiometric amounts of oxidant might therefore benefit the overall result. All these factors have been taken into account in the synthesis of bicyclic /-lactone 56, which has been obtained from cyanoacetic acid and 1,3-cyclohexadiene in 78% yield within 15 min reaction time (equation 25)60,88. 

Hwu et al. have examined the dependence of the metal oxidant on the mode of reactivity in silicon-controlled allylation of 1,3-dioxo compounds [95JOC856]. The use of manganese(III) acetate furnished the dihydrofuran product 22 only. On the other hand, use of cerium(IV) nitrate resulted in the formation of both acyclic (23) as well as the cyclized compound, with the product distribution dependent on the nature of the allylsilane. Facile synthesis of dihydrofurans by the cerium(IV) mediated oxidative addition of 1,3-dicarbonyl compounds to cyclic and acyclic alkenes has also been reported [95JCS(P1)187]. 

Manganese acetate-promoted oxidative addition of 1,3-dicarbonyl compounds (351) to endo-cyclic enol ethers (352) and enol lactones (353) gives 2,3,3a,6a-tetrahydrofuro[2,3-6]furan derivatives (354) and (355) <87CL223, 91TL711, 91TL7107). 

Manganese(III) can oxidize carbonyl compounds and nitroalkanes to carboxy-methyl and nitromethyl radicals [186]. With Mn(III) as mediator, a tandem reaction consisting of an intermolecular radical addition followed by an intramolecular electrophilic aromatic substitution can be accomplished [186, 187). Further Mn(III)-mediated anodic additions of 1,3-dicarbonyl and l-keto-3-nitroalkyl compounds to alkenes and alkynes are reported in [110, 111, 188). Sorbic acid precursors have been obtained in larger scale and high current efficiency by a Mn(III)-mediated oxidation of acetic acid acetic anhydride in the presence of butadiene [189]. Also the nitromethylation of benzene can be performed in 78% yield with Mn(III) as electrocatalyst [190]. A N03 radical, generated by oxidation of a nitrate anion, can induce the 1,4-addition of aldehydes to activated olefins. NOj abstracts a hydrogen from the aldehyde to form an acyl radical, which undergoes addition to the olefin to afford a 1,4-diketone in 34-58% yield [191]. 

Tsai AI, Lin CH, Chuang CP (2005) Manganese(III) acetate mediated oxidative free radical reactions between indole derivatives and 1,3-dicarbonyl compounds. Heterocycles 65 2381-... 

Since it is known that a-protons of the acylacetonitriles are more acidic than those of the methyl ketones, it was logical to use the acylacetonitrile building blocks during the first stage of the aldol-like condensation for the synthesis of heterocyclic compounds such as the 4H-pyran, 2-pyridone, and furan derivatives [85-95]. Therefore, it was expected that acylacetonitriles would be oxidized by manganese(III) acetate in a similar manner to the oxidation of a-cyanoacetic acid [65,96-99] and 1,3-dicarbonyl compounds [100] to give acylcyanomethyl radicals, CH(COR)CN, which would attack the alkenic double bonds to produce heterocyclic compoimds in one step [73,75,77,80,101-... 

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