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Over the past decades, studies of cyclic diacyl peroxides have shown superior or even fundamentally new reactivity compared to their acyclic counterparts in various reactions. Previously, the scope of cyclic diacyl peroxides was limited to the mono peroxy compounds. The first doubled cyclic diacyl peroxide is presented herein. The diperoxide was characterized by NMR spectroscopy, mass spectrometry, and IR spectroscopy. The structure of 4,4′-(butane-1,4-diyl)bis(4-methyl-1,2-dioxolane-3,5-dione) was confirmed by X-ray diffraction analysis. The novel diperoxide was prepared in a 55% overall yield in three steps from dibromobutane and diethyl methylmalonate. [ABSTRACT FROM AUTHOR]

Graphical abstract Malonyl peroxides were used for the one-pot construction of hybrid structures by conjugation of heterocycle (3 H -pyrazol-3-one, isoxazol-5(2 H)-one, pyrazolidine-3,5-dione, or barbituric acid) and amine or alcohol. The first stage represents oxidative C–O coupling with liberation of the carboxyl group which is functionalized at the second stage thus affording 'clicklike' products with malonic linker. [ABSTRACT FROM AUTHOR]

The reactions of O-electrophiles, such as organic peroxides, with carbon nucleophiles are an umpolung alternative to the common approaches to C-O bond formation. Nucleophilic substitution at the oxygen atom of cyclic diacyl peroxides by enol acetates with the following deacylation leads to α-acyloxyketones with an appended carboxylic acid in 28-87% yields. The effect of fluorinated alcohols on the oxidative functionalization of enol acetates by cyclic diacyl peroxides was studied experimentally and computationally. Computational analysis reveals that the key step proceeds as a direct substitution nucleophilic bimolecular (S N 2) reaction at oxygen (S N 2@O). CF 3 CH 2 OH has a dual role in assisting in both steps of the reaction cascade: it lowers the energy of the S N 2@O activation step by hydrogen bonding to a remote carbonyl and promotes the deacylation of the cationic intermediate.