Researchers from IOC RAS developed a method for the synthesis of organic peroxides, previously considered inaccessible

Currently, the intensive development of the chemistry of organic peroxides is mainly caused by their high biological activity. The main direction of medicinal chemistry of organic peroxides is the search for substances with activity against malaria and helminth infections. The discoverer of the natural peroxide Artemisinin, the Chinese pharmacologist Tu Youyou, was awarded in 2015 the Nobel Prize in physiology or medicine for her “discoveries in the treatment of malaria”. The efforts of synthetic chemists are currently aimed at the search for relatively simple synthetic peroxides, which are as active as their natural and semi-synthetic analogues, but much cheaper than them.

The development of methods for the synthesis of organic peroxides is complicated by the lack of experimental data and accumulated knowledge. Guided by existing concepts of organic chemistry, it is often impossible to assume the existence of certain classes of organic peroxides. Under such conditions, the tandem between synthetic chemists and specialists in calculation methods of analysis becomes necessary for the successful establishment of chemical laws in the field of organic peroxides.

The main pathways of organic peroxides decomposition, which chemists who work in the field of organic peroxides have to deal with, are various rearrangements, which occur under conditions, similar to those needed to obtain peroxides. One of the most widely known rearrangement of organic peroxides is the Baeyer-Villiger reaction.

 In this work, researchers from the Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences in collaboration with colleagues from Florida State University developed a method for the synthesis of a new class of organic peroxides, γ-peroxylactones, previously considered inaccessible. Researchers succeeded in establishing subtle patterns, which are responsible for the stability of organic peroxides of this class: stereoelectronic factors were determined, which contribute to the stability of the peroxide framework and prevent Baeyer-Villiger rearrangement.

The resulting γ-peroxylactones will be involved in studies conducted by laboratory № 13 of the Zelinsky Institute in collaboration with the All-Russian Research Institute of Phytopathology and D. I. MendeleevUniversity of Chemical Technology of Russia, on the development of native crops protection agents based on organic peroxides.

Source:

V. A. Vil',   Ya. Barsegyan,   L. Kuhn,   M. V. Ekimova,   E. A. Semenov,   A. Korlyukov,   A. O. Terent'ev  and  I. Alabugin, Synthesis of unstrained Criegee intermediates: inverse α-effect and other protective stereoelectronic forces can stop Baeyer-Villiger rearrangement of γ-hydroperoxy-γ-peroxylactones, Chem. Sci., 2020, accepted manuscript. DOI: 10.1039/D0SC01025A