gem-Bishydroperoxides

Introduction

The relevance of gem-dihydroperoxides to peroxidic antimalarial agents stimulated initial interest in this class of compounds.[1] [2] [3] [4] [5] Apart from their biological activities,[6,7] gem-dihydroperoxides have been established as important building blocks in synthetic chemistry, for example the preparation of organic peroxides, trioxanes, tetraoxanes, spirobisperoxyketals, and dicarboxylic diesters.[4] [7] [8] gem-Dihydroperoxides can also be employed as oxidizing agents under various conditions to perform transformations such as epoxidation[1] [2] [3] [4] [5] and sulfoxidation.[2] [3] [4] [5] [9] In addition, in situ decomposition of gem-dihydroperoxides can generate singlet oxygen as the active oxidant[8] [10] in olefin oxidation, for example.[11] The ability of gem-dihydroperoxides to generate radicals allows them to be furthermore exploited as radical initiators,[2] [3] [4] [5] for example methyl ethyl ketone peroxide is used in the manufacturing of acrylic resins, reinforced plastics, and unsaturated polyester resins.[6]

Itoh and co-workers established two catalyst-free preparative protocols for gem-dihydroperoxides, of which the one employs hydrogen peroxide[12] as terminal oxidant and the other molecular oxygen.[13] [14] The latter is achieved in combination with a photosensitizer (anthracene[13] or anthraquinone[14]) and exposure of the reaction mixture to light.

Reaction times can generally be reduced upon introduction of a catalyst, amongst which molecular iodine[15] as well as numerous transition-metal Lewis acids have proven effective.[4] [5] [8] [16] [17] Brønsted acids are comparably active as either homogeneous (sulfuric acid[3]) or heterogeneous catalysts, for example silica-sulfuric acid[2] or triflic-acid-functionalized silica-coated ferromagnetic nanoparticles.[18]

• References

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