Manufacturing technologies
Medicines, Organic electronic materials, Synthetic resins

Functionalization of perfluoroalkyl compounds by photocatalyst/
organostannanes mediated C–F bond activation
Department of Applied Chemistry, Graduate School of Engineering Innovative Catalysis Science Division, Institutefor Open and Transdisciplinary Research Initiatives (ICS-OTRI)Associate Professor Yoshihiro Nishimoto
Professor Makoto Yasuda

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以上AbstractC–F bonds are extremely strong; hence, the transformation ofthem under mild conditions is difficult, and the selective activationof a specific C–F bond from among multiple C–F bonds in perfluorinated compounds has not been achieved. In this study, theworld's first organic reaction that selectively converts a specificcarbon–fluorine (C–F) bond in perfluorinated compounds to otherfunctional groups. Experimental and theoretical results revealed
the importance of the cooperation of a photocatalyst and organotin compounds in this transformation. Organofluorine compounds
are attracting attention as pharmaceuticals, and this research isexpected to lead to the rapid synthesis of fluorine-containing drugs
from readily available perfluorinated compounds.

Manufacturing technologies▍ Background & Results
Fluorinated compounds are widely used in pharmaceuticals,
agricultural chemicals, functional resins, and organic electronicmaterials. In particular, perfluorinated compounds are attracting
attention because of their high thermal and chemical stability andvarious excellent properties such as water and oil repellency andchemical resistance. Since the carbon-fluorine bond is one of thestrongest of chemical bonds, its activation is a challenging issue inorganic chemistry and is being studied worldwide. In this research,
the site-selective C–F bond transformation to carbon-functionalgroups has been accomplished by using a photocatalyst andorganotin compounds under visible light irradiation. The establishment of the methodology to activate strong carbon-fluorine bonds
under such mild conditions is the key to achieving the selective
transformation of perfluorinated compounds. Both experimental
and theoretical experiments revealed that the cooperative actionof the photocatalyst and organotin compound are important in theprogression of the reaction. In particular, it is noteworthy that theorganotin compound plays the dual role of capturing unstable radical intermediates and scavenging fluorine as a Lewis acid, which
is a very significant finding for future research on carbon-fluorinebond conversion reactions. Furthermore, we have succeeded insynthesizing fluorine-substituted analogues of a compound thatshow promise for pharmaceutical applications.

▍ Significance of the research and Future perspective
Fluorine is a significant element in pharmaceuticals because
many small-molecule drugs contain fluorine atoms. It is expectedthat the field of fluorine-containing drugs will continue to grow. Asa result of this research, high valuable perfluorinated compounds,
which were impossible to synthesize in the past, can now be synthesized in a simple and short process, which is expected to leadto the expansion of the library of seed compounds for fluorine-containing drug discovery.

P a t e n t
Sugihara, Naoki; Nishimoto, Yoshihiro; Yasuda, Makoto et al. Photoredox-Catalyzed C–F Bond Allylation of Perfluoroalkylarenes at the Benzylic Position.
Journal of the American Chemical Society. 2021; 143(25): 9308-9313. doi: 10.1021/jacs.1c03760
https://pubs.acs.org/doi/10.1021/jacs.1c03760
https://resou.osaka-u.ac.jp/ja/research/2021/20210602_1
UR
L https://www.jst.go.jp/pr/announce/20210602-2/index.html
https://www.eurekalert.org/news-releases/628997
https://www.chem-station.com/blog/2021/08/c-f.html
K e y w o r d photocatalyst, stannane, fluorine compound, C–F bond activation
Tr e a t i s e