Autoxidation of Grignard reagents

The autoxidation of Grignard reagents can be diverted from its usual production of alcohols and be made to give hydroperoxides if the... 

The autoxidation of Grignard reagents was shown to be a two-step process ... 

The autoxidation of Grignard reagents or dialkylmercurials proceeds by a free radical chain mechanism involving the attack of ROO upon RMgX (Walling and Buckler, 1955 Lamb et al., 1966) or R2Hg (Razuvaev et al., 1960 Aleksandrov et al., 1964). These reactions may well involve electron transfer or at least a transition state for the formal Sh2 substitution reaction resembling [1]... 

Hydroperoxides have been obtained from the autoxidation of alkanes, aralkanes, alkenes, ketones, enols, hydrazones, aromatic amines, amides, ethers, acetals, alcohols, and organomineral compounds, eg, Grignard reagents (10,45). In autoxidations involving hydrazones, double-bond migration occurs with the formation of hydroperoxy—azo compounds via free-radical chain processes (10,59) (eq. 20). 

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