The reasons for the anomalous stability of bis-peroxides are discovered



Gabriel dos Passos Gomes, a graduate student from the Alabugin Group, in collaboration with researchers from the Russian Academy of Sciences, provided an explanation to unusual stability of bis-peroxides in a recent paper on "Stereoelectronic source of the anomalous stability of bis-peroxides” published on Chemical Science (Chem. Sci., 2015, 6, 6783, DOI: 10.1039/c5sc02402a).
 
The peroxide functionality is often perceived (and deservingly so) as a dangerous highly reactive group balancing on the brink of stability. This paper explained why combining two unstable peroxides in a single molecule can lead to paradoxically stable compounds that can melt well above 100°C without decomposition. Gabriel’s analysis revealed that the anomeric effect, a well-known stereoelectronic phenomenon from carbohydrate chemistry finds a reincarnation in bis-peroxides. This study had a broader implications because it also showed that any peroxide separated from an appropriate
electron-accepting C–X bond by one-atom bridge should be stabilized.
 
The direct connection between these findings and the origins of the increased stability of Artemisinin, an antimalarial natural product that bears a peroxide moiety stabilized by an adjacent C-O sigma-acceptor, received significant attention after the announcement of the 2015 Nobel Prize in Medicine for the discovery of Artemisinin. Gabriel’s work was featured in the Royal Society of Chemistry’s online magazine, Chemistry World and highlighted at the NBO website.


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