The mechanism of the singlet oxygen ene reaction has been a subject of renewed interest within the last few years. The main question being whether this reaction proceeds through a concerted mechanism or if it involves discrete intermediates. In general, the majority of experimental and computational studies support a traditional stepwise mechanism involving a perepoxide‐like intermediate. In this minireview we highlight the most prominent and recent theoretical, as well as experimental results relating to the challenging mechanism of the singlet oxygen ene oxyfunctionalization.

The formation of one-dimensional coordination polymers of cyano-substituted porphyrin derivatives on Au(111) induced by thermal annealing is demonstrated by means of scanning tunnelling microscopy. The polymer is stabilised by an unusual threefold coordination motif mediated between an Au atom and the cyano groups of the porphyrin derivatives.

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A new general reaction for the preparation of isomerically pure hydroxyalkylated C(60) monoadducts, via the free radical photochemical addition of alcohols to [60]fullerene, is described.

Cyclopropyl-substituted olefins are employed as mechanistic probes in the singlet oxygen−alkene ene reaction. In MeOH and aprotic solvents [CHCl3, (CH3)2CO, CH3CN], only the allylic hydroperoxides bearing an intact cyclopropyl group are detected. The reaction mechanism is independent of solvent polarity. Our findings, to a certain experimental limit, exclude a biradical or dipolar intermediate.

The stereochemistry of the allylic oxidation (ene reaction) mediated by singlet oxygen ((1)O2), using the optically active alkene (S,S)-cis-1,4-diphenyl-2-butene-1,4-d2 , in MeOH and aprotic solvents was investigated. Our findings indicate that the title reaction is a highly stereospecific suprafacial process, independent of solvent polarity. The observation of an isotope effect, which matches the stereogenic ratio exactly, rules out biradical or open dipolar intermediates.