《Desymmetrization of difluoromethylene groups by C-F bond activation》 was published in Nature (London, United Kingdom) in 2020. These research results belong to Butcher, Trevor W.; Yang, Jonathan L.; Amberg, Willi M.; Watkins, Nicholas B.; Wilkinson, Natalie D.; Hartwig, John F.. Application In Synthesis of Diethyl 2-methylmalonate The article mentions the following:
Tertiary stereogenic centers containing one fluorine atom are valuable for medicinal chem. because they mimic common tertiary stereogenic centers containing one hydrogen atom, but they possess distinct charge distribution, lipophilicity, conformation and metabolic stability1-3. Although tertiary stereogenic centers containing one hydrogen atom are often set by enantioselective desymmetrization reactions at one of the two carbon-hydrogen (C-H) bonds of a methylene group, tertiary stereocenters containing fluorine have not yet been constructed by the analogous desymmetrization reaction at one of the two carbon-fluorine (C-F) bonds of a difluoromethylene group3. Fluorine atoms are similar in size to hydrogen atoms but have distinct electronic properties, causing C-F bonds to be exceptionally strong and geminal C-F bonds to strengthen one another4. Thus, exhaustive defluorination typically dominates over the selective replacement of a single C-F bond, hindering the development of the enantioselective substitution of one fluorine atom to form a stereogenic center5,6. Here the authors report the catalytic, enantioselective activation of a single C-F bond in an allylic difluoromethylene group to provide a broad range of products containing a monofluorinated tertiary stereogenic center. By combining a tailored chiral iridium phosphoramidite catalyst, which controls regioselectivity, chemoselectivity and enantioselectivity, with a fluorophilic activator, which assists the oxidative addition of the C-F bond, these reactions occur in high yield and selectivity. The design principles proposed in this work extend to palladium-catalyzed benzylic substitution, demonstrating the generality of the approach. In the experimental materials used by the author, we found Diethyl 2-methylmalonate(cas: 609-08-5Application In Synthesis of Diethyl 2-methylmalonate)
Diethyl 2-methylmalonate(cas: 609-08-5) belongs to aliphatic hydrocarbons. Aliphatic hydrocarbons belong to the most abundant fraction in crude oil. Aliphatics molecules are linear or branched open-chain structures such as n-alkanes, isoalkanes, cycloalkanes (naphthenes), terpenes and steranes.Application In Synthesis of Diethyl 2-methylmalonate
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics