ZIOC researchers have discovered a method for the functionalization of inert C-H bonds using the nickel / diacyl peroxide system

Metal complex catalysis is currently one of the most promising approaches to the synthesis of organic compounds. Many chemists are familiar with palladium-based catalyst systems: their discovery was awarded the 2010 Nobel Prize in Chemistry and is now used in industries ranging from drug synthesis to materials manufacturing. Nickel may seem like just a poor relative of palladium in the field of transition metal catalysis. However, the ability to be in various oxidation states, the tendency to one-electron transitions, as well as the low cost and safety makes nickel catalysis a powerful tool for the formation of new chemical bonds.

Scientists of the Zelinsky Institute together with colleagues from Florida State University, have developed a mechanistically and conceptually rich approach to the oxidative acyloxylation of Csp3-H bonds using the nickel/diacyl peroxide system. Diacyl peroxide and a nickel salt were used to create dynamically interconverting Ni(III) catalytic particles bearing a carboxylate radical.

Transformations of diacyl peroxide/metal systems typically begin with the formation of O-centered carboxylate radicals, however, such radicals undergo rapid fragmentation to form alkyl radicals. The authors of the work succeeded in finding mechanisms capable of stopping decarboxylation and preserving the carboxylate radical for the activation of C–H bonds. Thus, the ability of cyclic peroxides to participate in the chemistry of high-valent nickel has been shown for the first time. This discovery illustrates the rich potential of organic peroxides to develop new reactions.

An article based on the results of this study was published in a special issue of Organometallics dedicated to the 90th anniversary of the outstanding chemist, Academician of the Russian Academy of Sciences Irina P. Beletskaya.

This work was supported by the Russian Science Foundation grant 21-73-10016.

Source:

Vera A. Vil’, Yana A. Barsegyan, Leah Kuhn, Alexander O. Terent’ev, Igor V. Alabugin Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)−H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides // Organometallics, 2023, accepted manuscript. DOI: 10.1021/acs.organomet.2c00663.