Chemiluminescence-promoted oxidation of alkyl enol ethers by NHPI under mild conditions and in the dark.

The hydroperoxidation of alkyl enol ethers using -hydroxyphthalimide and molecular oxygen occurred in the absence of catalyst, initiator, or light. The reaction proceeds through a radical mechanism that is initiated by -hydroxyphthalimide-promoted autoxidation of the enol ether substrate. The resulting dioxetane products decompose in a chemiluminescent reaction that allows for photochemical activation of -hydroxyphthalimide in the absence of other light sources.

FINO initiates ferroptosis through GPX4 inactivation and iron oxidation.

Ferroptosis is a non-apoptotic form of regulated cell death caused by the failure of the glutathione-dependent lipid-peroxide-scavenging network. FINO is an endoperoxide-containing 1,2-dioxolane that can initiate ferroptosis selectively in engineered cancer cells. We investigated the mechanism and structural features necessary for ferroptosis initiation by FINO.

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

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.