Synthesis of five- and six-membered cyclic organic peroxides: Key transformations into peroxide ring-retaining products

Abstract

SummaryThe present review describes the current status of synthetic five and six-membered cyclic peroxides such as 1,2-dioxolanes, 1,2,4-trioxolanes (ozonides), 1,2-dioxanes, 1,2-dioxenes, 1,2,4-trioxanes, and 1,2,4,5-tetraoxanes. The literature from 2000 onwards is surveyed to provide an update on synthesis of cyclic peroxides. The indicated period of time is, on the whole, characterized by the development of new efficient and scale-up methods for the preparation of these cyclic compounds. It was shown that cyclic peroxides remain unchanged throughout the course of a wide range of fundamental organic reactions. Due to these properties, the molecular structures can be greatly modified to give peroxide ring-retaining products. The chemistry of cyclic peroxides has attracted considerable attention, because these compounds are used in medicine for the design of antimalarial, antihelminthic, and antitumor agents.

Catalyst Development for the Synthesis of Ozonides and Tetraoxanes Under Heterogeneous Conditions: Disclosure of an Unprecedented Class of Fungicides for Agricultural Application

“…Peroxidation of ketones with hydrogen peroxide opened access to the synthesis of various classes of peroxides, such as geminal bis‐peroxides, geminal bis‐hydroperoxides, β‐hydroxy‐hydroperoxides, tetraoxanes, cyclic triperoxides, or tricyclic monoperoxides . The peroxidation of monoketones and their derivatives has been studied in detail,‐ whereas the peroxidation of diketones was studied much less, which is associated with the formation of complex mixtures of inseparable peroxide products. For this reason, the selective synthesis of peroxides on the basis of diketones is a very difficult task.…”

Mn(OAc)3 catalyzed intermolecular oxidative peroxycyclization of naphthoquinone

“…8 They are based on three key reagents: oxygen, ozone and hydrogen peroxide. In particular, synthesis of 1,2-dioxanes can be realized with oxygen.…”

Selective Inhibitors of Glutathione Transferase P1 with Trioxane Structure as Anticancer Agents

“…A series of seven 1,2,4‐trioxanes, derived from the reported compound 2 ,33 bearing a 6‐substituent with an α,β‐unsaturated aromatic ester moiety, was synthesized by type II photooxygenation and peroxyacetalization starting from allylic alcohols (Scheme ). This photochemical approach allows the synthesis of a variety of substitution patterns at the 1,2,4‐trioxane ring 31. The synthesis of α,β‐unsaturated aromatic ester trioxanes was first described by Griesbeck et al.…”

“…The underlying mechanisms for the anticancer activity of artemisinin are still under discussion; however, the 1,2,4‐trioxane group of the molecule has been demonstrated to be essential for its reported biological activities 30. Within the last three decades, a remarkable collection of derivatives of the basic 1,2,4‐trioxane peroxide skeleton has been developed 31…”