Catalyst-Controlled Dioxygenation of Olefins: An Approach to Peroxides, Alcohols, and Ketones

Abstract

An efficient catalytic approach for the synthesis of substituted peroxides, alcohols, and ketones through a catalyst-controlled highly selective dioxygenation of olefins has been demonstrated. The reported methods are mild and practical, can be switched by the selection of different catalytic systems, and employ peroxide as an oxidant and a reagent at room temperature.

Recent Advances in Radical Dioxygenation of Olefins

“…[17] In the case of -methylstyrene, a 3:1 mixture of diastereoisomers was formed in 32 % yield. [17] In the case of -methylstyrene, a 3:1 mixture of diastereoisomers was formed in 32 % yield.…”

“…[17] Reactions of cyclic and acyclic olefins were performed at room temperature with 35-70 % yields. [17] Reactions of cyclic and acyclic olefins were performed at room temperature with 35-70 % yields.…”

“…[17] A series of substituted olefins containing either electron-donating or electron-withdrawing groups delivered the desired alcohols in high yields. [17] A series of substituted olefins containing either electron-donating or electron-withdrawing groups delivered the desired alcohols in high yields.…”

Hypervalent iodine compounds for anti-Markovnikov-type iodo-oxyimidation of vinylarenes

“…Growth of interest is observed concerning the reactions of styrenes with imide- N -oxyl radicals, in which the latter add to the terminal position of the double C=C bond with the formation of stabilized benzyl radicals, which undergo the subsequent functionalization. In the presence of oxygen or tert -butyl hydroperoxide, oxidation proceeds to form the C–O [46–51] or the C=O [52–55] moiety. More complex reagents and reaction systems allows to form C–C [56–57] and C–N [58–59] bonds.…”

CuI‐Catalyzed Synthesis of Propargyl Hydroperoxides Using Molec­ular Oxygen and Hydroxylamines

“…[8–10,14–18] Controlling the oxidation state of the resulting products, however, remains challenging (Figure 2). Although ketones14,15 like 4 and alcohols16,17 like 5 can be prepared in high yield, a general method has not been reported to synthesize and isolate the intermediate hydroperoxide 3 in appreciable quantities. These hydroperoxides are of particular interest due to the biological activities associated with both synthetic and naturally occurring peroxides 19,20…”