Synthesis of 1-hydroperoxy-1 '-alkoxyperoxides by the iodine-catalyzed reactions of geminal bishydroperoxides with acetals or enol ethers

It was found that iodine-catalyzed reactions of geminal bishydroperoxides with acetals proceed with the replacement of only one alkoxy group by the peroxide group to give previously unknown structures of 1-hydroperoxy-1'-alkoxyperoxides in yields up to 64%. The same compounds are formed in the iodine-catalyzed reactions of geminal bishydroperoxides with enol ethers. The nature of the solvent has a decisive influence on the formation of 1-hydroperoxy-1'-alkoxyperoxides. In the series of Et2O, THF, EtOH, CHCl3, CH3CN, and hexane, the best results were obtained with the use of Et2O or THF as the solvent.