Novel Fluorinated Biphenyl Compounds Synthesized via Pd(0)-Catalyzed Reactions: Experimental and Computational Studies

Muhammad Atta Ur Rehman; Muhammad Adeel; Saad M Alshehri; Ume Aiman; Alexander Villinger; Saifullah Bullo; Rabia Baby; Muhammad Adnan Asghar; Aleksey E Kuznetsov; Muhammed Lamin Sanyang

doi:10.1021/acsomega.3c01993

Novel Fluorinated Biphenyl Compounds Synthesized via Pd(0)-Catalyzed Reactions: Experimental and Computational Studies

ACS Omega. 2023 Aug 5;8(32):29414-29423. doi: 10.1021/acsomega.3c01993. eCollection 2023 Aug 15.

Affiliations

¹ Institute of Chemical Sciences, Gomal University, Dera Ismail Khan 29220, Khyber Pukhtoon Khuwa, Pakistan.
² Department of Chemistry, College of Science, King Saud University, Riyadh 11451, Saudi Arabia.
³ Institute of Chemistry, Department of Inorganic Chemistry, University of Rostock, Albert Einstein Strasse, 18059 Rostock, Germany.
⁴ Department of Human and Rehabilitation Sciences, Begum Nusrat Bhutto Women University, Sukkur 65200, Sindh, Pakistan.
⁵ Department of Education, Sukkur IBA University, Sukkur 65200, Pakistan.
⁶ Department of Chemistry, Division of Science and Technology, University of Education Lahore, Lahore 89002, Pakistan.
⁷ Departamento de Química, Campus Santiago Vitacura, Universidad Técnica Federico Santa María, Avenue Santa María 6400, Vitacura 7660251, Chile.
⁸ Directorate of Research and Consultancy, University of The Gambia, Kanifing Campus, MDI Road, P.O Box 3530, Serrekunda 3530, The Gambia.

Abstract

Five new difluorinated biphenyl compounds, 4'-(tert-butyl)-3,4-difluoro-1,1'-biphenyl (TBDFBP), 1-(3',4'-difluoro-[1,1'-biphenyl]-4-yl)ethanone (DFBPE), 3',4'-difluoro-2,5-dimethoxy-1,1'-biphenyl (DFDMBP), 3,4-difluoro-3'-nitro-1,1'-biphenyl (DFNBP), and (3',4'-difluoro-[1,1'-biphenyl]-3-yl)(methyl)sulfane (DFBPMS), have been successfully synthesized by the well-known Suzuki-Miyaura coupling with excellent yields averaging 78%. UV-visible, Fourier transform infrared ,and ¹³C NMR and ¹H NMR spectroscopies along with single-crystal X-ray diffraction (SC-XRD) analysis (for TBDFBP and DFBPE) were used for the structure elucidation of the synthesized compounds. The SC-XRD results demonstrated the crystal systems of the studied compounds, TBDFBP and DFBPE, to be monoclinic, and their space groups were found to be P2₁/c. Also, a detailed density functional theory study was performed. The calculated structures for TBDFBP and DFBPE were found to agree quite well with the experimental results. The natural bonding orbital charge analysis suggested that molecules of these compounds should interact quite noticeably with each other in the solid phase and with polar solvent molecules. Molecular electrostatic potential analysis suggests that accumulation of positive and negative potential implies possibility of quite significant dipole-dipole intermolecular interactions in crystals of these compounds, as well as quite strong interactions with polar solvent molecules. The global reactivity parameters analysis suggests all compounds to be quite stable in redox reactions, with the compound DFNBP being relatively more reactive and the compounds TBDFBP and DFDMBP being relatively more stable.