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2021-07-05 13:16:57

New stable 2-fluoroallyl electrophiles were synthesized in the Zelinsky Institute

Fluorinated bioisosteres have found a broad application in modern drug design. In particular, a fluoroalkene moiety can efficiently mimic an amide bond due to a similarity in the electronic and steric parameters, thus increasing the hydrolytic stability, lipophilicity, and permeability through membranes. As a result, by using such bioisosteric replacement, one could substantially improve the efficiency of biologically active compounds known to date. Among the methods for the preparation of fluoroalkenes and compounds containing a 2-fluoroallyl fragment, one of the most convenient is ring opening in fluoro-substituted cyclopropanes. However, its synthetic application has been limited for a long time due to the difficulty of controlling the regio- and stereoselectivity of nucleophile addition to 2-fluoroallyl-cationic structures, which are key intermediates in these processes.

In the Laboratory of Chemistry of Diazo Compounds of the ZIOC RAS, new stable 2-fluoroallyl electrophiles (2-fluoroallyl)pyridinium tetrafluoroborates were synthesized by the opening of gem-bromofluorocyclopropanes. Palladium-catalyzed reactions of these salts with amines, malonates, and boronic acids open the way to a wide range of functionalized compounds with a fluoroallyl moiety. All developed transformations proceed with high regio- and stereoselectivity.

 

Source:

Angelina Yu. Bobrova, Maxim A. Novikov, and Yury V. Tomilov (2-Fluoroallyl)pyridinium tetrafluoroborates: novel fluorinated electrophiles for Pd-catalyzed allylic substitution Org. Biomol. Chem., 2021, 19, 4678-4684. DOI: 10.1039/D1OB00567G.

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The European Academy of Sciences (Academia Europaea) was founded in 1988. It unites about four thousand globally acknowledged experts in mathematics, medicine, natural sciences, humanities, law, economy, and social and political sciences from many countries of Europe. Among its members are also European scientists who live in other regions of the world. Currently, it includes seventy two Nobel laureates and it should be highlighted that many of them were elected to the Academy before winning the Prize.
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