Copper(I)-Catalyzed Oxidation of Alkenes Using Molecular Oxygen and Hydroxylamines: Synthesis and Reactivity of α-Oxygenated Ketones

Abstract

The copper(I)-catalyzed oxidation of alkenes with molecular oxygen and N-hydroxyphthalimide (NHPI) or N-hydroxybenzotriazole (HOBt) provided α-oxygenated ketones. The reaction proceeded under a balloon of O2 at room temperature to furnish the dioxygenated products in 50-90% yield. These compounds, particularly the HOBt derivatives, can be further functionalized with phosphorus, nitrogen, and sulfur nucleophiles to give synthetically useful products.

Regio‐ und chemoselektive Oxo‐Azidierung von Vinylarenen, katalysiert durch Kupfer(II) und sichtbares Licht

“…[1,2] In Kombination mit photoredox-aktiven Cu I -Komplexen [3] wurde sie zu einem wirkungsvollen Mittel der Difunktionalisierung [4] von C-C-Mehrfachbindungen, was eine vielversprechende Alternative zur thermischen Aktivierung durch Übergangsmetalle [5] oder organische Oxidationsmittel bietet. [1,2] In Kombination mit photoredox-aktiven Cu I -Komplexen [3] wurde sie zu einem wirkungsvollen Mittel der Difunktionalisierung [4] von C-C-Mehrfachbindungen, was eine vielversprechende Alternative zur thermischen Aktivierung durch Übergangsmetalle [5] oder organische Oxidationsmittel bietet.…”

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

“…The oxidations of enynes to propargylic peroxides using oxygen and NHPI involved substantial modification of the conditions used to synthesize ketones 15,27. Because the synthesis of ketones such as 4 (Figure 2) likely involves hydroperoxides 3 as intermediates, we considered that the reaction conditions could be modified to allow for the selective production of the desired hydroperoxide.…”

“…[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…”

Recent Advances in Radical Dioxygenation of Olefins

“…[16] The oxidation of a series of styrenes and enynes in high yields was demonstrated. [16] The oxidation of a series of styrenes and enynes in high yields was demonstrated.…”

“…[16] In addition, α-bromostyrene can be oxidized to the α-oxygenated ketone in high yield. [16] In addition, α-bromostyrene can be oxidized to the α-oxygenated ketone in high yield.…”