biostudies-literatureUnknown6Chen WJDensity functional theory calculations have been performed to study the detailed mechanism of Ni-mediated [3+2] cycloaddition of 2-trifluoromethyl-1-alkenes with alkynes via cleavage of two C-F bonds. It was found that the reaction pathway involves oxidative cyclization, the first β-fluorine elimination, and then intramolecular 5-endo insertion of difluoroalkene, followed by the second cleavage of C-F bond, and finally the dissociation of difluorides yields the fluorine-containing product cyclopentadienes in sequence. The overall rate-determining step is the combined processes of the β-fluorine elimination and the 5-endo insertion. Furthermore, we investigated the effect of different ligands and the regioselectivity of asymmetric alkynes. The detailed energy profiles aFrontiers in chemistry319https://www.ebi.ac.uk/biostudies/studies/S-EPMC6099089biostudies-literatureDFT Studies on Ni-Mediated C-F Cleavage for the Synthesis of Cyclopentadiene Derivatives.PMC6099089Xu RNWang BWu QHHuang XLin WSun XChen WJfalseDFT Studies on Ni-Mediated C-F Cleavage for the Synthesis of Cyclopentadiene Derivatives.Density functional theory calculations have been performed to study the detailed mechanism of Ni-mediated [3+2] cycloaddition of 2-trifluoromethyl-1-alkenes with alkynes via cleavage of two C-F bonds. It was found that the reaction pathway involves oxidative cyclization, the first β-fluorine elimination, and then intramolecular 5-endo insertion of difluoroalkene, followed by the second cleavage of C-F bond, and finally the dissociation of difluorides yields the fluorine-containing product cyclopentadienes in sequence. The overall rate-determining step is the combined processes of the β-fluorine elimination and the 5-endo insertion. Furthermore, we investigated the effect of different ligands and the regioselectivity of asymmetric alkynes. The detailed energy profiles a2018-01-01T00:00:00Z20182025-04-19T06:28:03.811Z2019-03-26T23:52:55ZS-EPMC60990893015136110.3389/fchem.2018.00319