ZIOC Researchers have developed a new approach to the difunctionalization of alkenes using fluorinated compounds

Alkenes are a class of readily available starting compounds for laboratory and industrial organic synthesis. The difunctionalization of alkenes is an efficient approach to greatly increase molecular complexity in a minimum number of synthetic steps. To implement this approach, radical reactions are often used, which have unique chemoselectivity and are compatible with a variety of functional groups. In recent years, photoredox catalysis has been increasingly used to initiate free radical transformations, which makes it possible to generate these intermediates under mild conditions.

Scientists from the Laboratory of Functional Organic Compounds of the ZIOC under the conditions of dual catalysis, managed to realize the process of difunctionalization of alkenes with the participation of fluorinated organic halides, as well as S-centered nucleophiles or iodide anions, using a cyanoarene-type photocatalyst and a copper (I) complex. Presumably, during the photocatalytic cycle, fluorinated radicals are generated, and the copper complex promotes the formation of a carbon-heteroatom bond due to the interception of the resulting radicals by copper sulfide or iodide species. Thiazolinyl- and perfluoropyridinylthiolates were used as S-nucleophiles, and the sulfides formed in the reaction can be further transformed through C-S bond cleavage under photocatalytic conditions. Thus, the overall developed process of alkenes difunctionalization proceeds with the formation of two C–C bonds and leads to the production of polyfunctional organofluorine compounds that are difficult to access by other methods.
 

Source:

Vladislav S. Kostromitin, Vitalij V. Levin, Alexander D. Dilman Dual Photoredox/Copper Catalyzed Fluoroalkylative Alkene Difunctionalization // J. Org. Chem. 2023, accepted manuscript. DOI: 10.1021/acs.joc.3c00448.