《C-F bond arylation of fluoroarenes catalyzed by Pd0 phosphine complexes: theoretical insight into regioselectivity, reactivity, and prediction of ligands》 was written by Zhong, Rong-Lin. Recommanded Product: Methyl 4-fluorobenzoate And the article was included in Organic Chemistry Frontiers in 2020. The article conveys some information:
Palladium-catalyzed C-F bond arylation of pentafluorobenzene was theor. investigated as an example of aryl-F bond functionalization. DFT computations show that C3-regioselective arylation of pentafluorobenzene occurs more favorably than C1 and C2-ones as reported exptl., through oxidative addition of the C-F bond to Pd0 species, transmetalation and reductive elimination of the C-C bond. Oxidative addition of the C-F bond is the rate-determining and regioselectivity-determining step. The lower energy transition state of the oxidative addition of the C3-F bond (TS-C3) arises from a larger stabilization energy between Pd0(BrettPhos) and distorted pentafluorobenzene moieties in TS-C3 than those in TS-C1 and TS-C2. The larger stabilization energy is a result of a lower σ* orbital energy of the distorted C3-F bond than those of C1-F and C2-F bonds, which leads to a larger charge transfer from the Pd dπ orbital to the σ* orbital of the C3-F bond. The results suggest that both σ* orbital energy and bond dissociation energy are important factors for determining the reactivity of the C-F bond. Also, the activation barriers of the C-F bond with different substitution groups follow the order: NO2 < COOMe < CN ~CF3 < F, which is approx. consistent with the order of electron-withdrawing ability of these groups. It is theor. predicted here that NMe2-substituted BrettPhos is better for C-F bond cleavage than BrettPhos, where three NMe2 groups are introduced to BrettPhos instead of the iso-Pr groups. The experimental part of the paper was very detailed, including the reaction process of Methyl 4-fluorobenzoate(cas: 403-33-8Recommanded Product: Methyl 4-fluorobenzoate)
Methyl 4-fluorobenzoate(cas: 403-33-8) can be used in the synthesis of trisubstituted imidazole derivatives containing a 4-fluorophenyl group, a pyrimidine ring, and a CN- or CONH2-substituted benzyl moiety.Recommanded Product: Methyl 4-fluorobenzoate
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