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DFT Studies on Ni-Mediated C-F Cleavage for the Synthesis of Cyclopentadiene Derivatives.

ABSTRACT: 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 ?-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 ?-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 and structures are presented in this study.

SUBMITTER: Chen WJ

PROVIDER: S-EPMC6099089 | biostudies-literature | 2018

REPOSITORIES: biostudies-literature

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DFT Studies on Ni-Mediated C-F Cleavage for the Synthesis of Cyclopentadiene Derivatives.

Chen Wen-Jie WJ Xu Ruo-Nan RN Lin Weimin W Sun Xuejiao X Wang Bin B Wu Qi-Hui QH Huang Xin X

Frontiers in chemistry 20180813

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 <i>β</i>-fluorine elimination, and then intramolecular 5-<i>endo</i> insertion of difluoroalkene, followed by the second cleavage of C-F bond, and finally the dissociation of difluorides yields the fluorine-containing ...[more]

PMID: 30151361

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