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

Frontiers in Chemistry

Bin Wang¹  Ruo-Nan Xu¹  Xin Huang¹  Wen-Jie Chen²  Weimin Lin²  Xuejiao Sun²  Qi-Hui Wu² 

[1] Department of Chemistry, College of ChemistryFuzhou University, Fuzhou, China;Department of Material Chemistry, College of Chemical Engineering and Materials ScienceQuanzhou Normal University, Quanzhou, China;

关键词: DFT studies;    Ni-mediated;    C-F cleavage;    cyclopentadiene derivative;    regioselectivity;   

DOI  :  10.3389/fchem.2018.00319

来源: DOAJ

【 摘 要 】

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 and structures are presented in this study.

【 授权许可】

Unknown