Peroxymercuration-demercuration

Eq. 34). The resultant p-mercurioalkyl peroxides can often be demercurated with sodium borohydride (Eq. 35), or by brominolysis (Eq. 36) without substantial cleavage of the 0-0 bond. Both peroxymercuration and demercurations occur rapidly under mild conditions 48). 

Use of mild conditions was crucial and the development of diimide reduction of singlet oxygenates, silver-salt-assisted displacement of halide by peroxide nucleophiles, peroxymercuration and demercuration, peroxide transfer from organotin to alkyl triflates, and oxygen trapping of azoalkane-derived diradicals have all played a part in providing the rich harvest of new bicyclic peroxides described herein. 

With mercury(II) nitrate, the five-membered ring peroxide was obtained as an approximately equimolar mixture of isomers, while the 1,2-dioxacyclohexane contained about three times as much trans- as ds-isomer. Peroxymercuration of alkyl-substituted 1,4-penta- and 1,5-hexadienes, followed by demercuration, afforded mixtures of isomeric cyclic alkyl peroxides in yields strongly dependent on the number and position of the substituents175. 

The peroxymercuration-demercuration of alkenes provides a more versatile approach to the corresponding hydroperoxides or dialkyl peroxides than direct acid-catalyzed addition (equation 239).372 374... 

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