1,1-Dihydroperoxides

Gem-dihydroperoxides (g-DHPs), often referred to as 1,1-dihydroperoxides, are a class of molecules of interest because of their reactivity as well as their utility as synthetic reagents and intermediates. This review begins with a listing of previous reviews and commercially available g-DHPs, followed by a brief discussion of safety and regulatory issues. The properties of g-DHPs are then overviewed, with an emphasis on the physical properties, biological activity, thermal stability, spectroscopic properties, and behavior on chromatographic media. The remaining sections describe the synthesis and reactions of g-DHPS. The largest of these sections describes the various methods for synthesis of g-DHPs based upon class of catalyst or reagent and compares applications of different reagents selected target skeletons. One of the most significant applications of g-DHPs, their use as precursors for 1,2,4,5-tetraoxanes, is discussed in detail, including tabular comparisons of approaches to selected skeletons. The chapter concludes with a discussion of other important reactions of g-DHPs, including alkylations, nucleophilic and electrophile-promoted additions to alkenes, acetalizations, acylations and acylation-promoted fragmentations, acid-promoted dimerizations and decompositions, silylations, and application as oxygen transfer agents. Keywords: cylation; alkylation; Bronsted acid; 1,1-dihydroperoxide; gem-dihydroperoxide; hydrogen peroxide; Lewis acid; synthesis; silylation; 1,2,4,5-tetraoxane