Despite the fact that extensive research has been carried out, the oxygenation of alkyl magnesium species still remains a highly unexplored research area and significant uncertainties concerning the mechanism of these reactions and the composition of the resulting products persist. This case study compares the viability of the controlled oxygenation of alkylmagnesium complexes supported by β-diketiminates. The structural tracking of the reactivity of (N,N)MgR-type complexes towards O at low temperature showed that their oxygenation led exclusively to the formation of magnesium alkylperoxides (N,N)MgOOR. The results also highlight significant differences in the stability of the resulting alkylperoxides in solution and demonstrate that [(BDI)Mg(μ-η :η -OOBn)] (in which BDI=[(ArNCMe) CH] and Ar=C H iPr -2,6) can be easily transformed to the corresponding magnesium alkoxide [(BDI)MgOBn] at ambient temperature, whilst [( BDI)Mg(μ-OOtBu)] (in which BDI=[(ArNCMe) CH] and Ar=C H F -2,4,6) is stable under similar conditions. The observed selective oxygenation of (N,N)MgR-type complexes to the corresponding (N,N)MgOOR alkylperoxides strongly contradicts the widely accepted radical-chain mechanism for the oxygenation of the main-group-metal alkyls. Furthermore, either the observed transformation of the alkylperoxide [(BDI)MgOOBn] to the alkoxide [(BDI)MgOBn] as well as the formation of an intractable mixture of products in the control reaction between the alkylperoxide [( BDI)MgOOtBu] and the parent alkylmagnesium [( BDI)MgtBu] complex are not in line with the common wisdom that magnesium alkoxide complexes' formation results from the metathesis reaction between MgOOR and Mg-R species. In addition, a high catalytic activity of well-defined magnesium alkylperoxides, in combination with tert-butyl hydroperoxide (TBHP) as an oxygen source, in the epoxidation of trans-chalcone is presented.

A novel organozinc initiator with a clear mechanistic signature for organic radical reactions has been developed.

O what a reaction: The oxygenation of Me2Zn⋅tBu‐DAB (tBu‐DAB=1,4‐di‐tert‐butyl‐1,4‐diazabutadiene) affords the unprecedented oxo(methylperoxide) cubane 1, the corresponding double cubic oxo(methoxide) 2, and the CC coupled dinuclear methoxide [(MeZn)2(tBu‐DAB‐DAB(H)‐tBu)(μ‐OMe)], the formation of which involves initial ZnOOMe bond homolysis.

The epoxidation of enones by zinc alkylperoxides is a challenging task receiving considerable attention in contemporary research; however, until now no welldefined zinc alkylperoxide based systems have been described. Here, a new catalytic method of epoxidation of enones in the presence of zinc alkylperoxides supported by N,N-bidentate ligands and tert-butyl hydroperoxide is reported. A new dimeric zinc alkylperoxide complex supported by an aminotroponiminate ligand is also presented. The studied catalytic systems show high activity in the epoxidation of trans-chalcone, and in the case of a chiral catalyst with the (S,S)-N,N′-bis(1-phenylethyl)aminotroponiminate ligand a moderate enantioselectivity was achieved.