Construction of Carbon‐Fluorine Bonds via Copper‐Catalyzed/‐Mediated Fluorination Reactions

Abstract

The construction of carbon-fluorine bonds is an important yet challenging task in organic synthesis. Transition metal-catalyzed/-mediated CÀ F bond forming processes have recently emerged as a viable strategy and provided access to value-added monofluorinated compounds. A dramatic increase in fluorination methods using inexpensive and earth-abundant copper can be seen in the past decade surpassing those using palladium and silver. This review discusses the recent development of Cu-catalyzed/-mediated formation of C(sp 2 )À F and C(sp 3 )À F bonds.

Mechanism of Cu-Catalyzed Iododeboronation: A Description of Ligand-Enabled Transmetalation, Disproportionation, and Turnover in Cu-Mediated Oxidative Coupling Reactions

“…AcO − induces boronate formation from the arylboronic acid, facilitating transmetalation to give initially [8] + that then adds I − to form 9. Disproportionation involving 9 and [3] + gives 11 as the most stable Cu(III) species along with Cu(I) species [10] + and so proceeds with loss of one phen ligand. 11 then undergoes reductive elimination, delivering the aryl iodide product and Cu(I) species 12.…”

“…There are several reported methods for Cu-catalyzed iododeboronation, each with subtle variations in the copper source, ligand, and associated reaction conditions. − Related copper-catalyzed or -mediated halodeboronation reactions, such as the equivalent fluorination reaction, also operate with similar reaction conditions. − This general reaction class therefore has broad applications across synthetic chemistry and specific applications in bio-facing fields.…”

Fluorine-a small magic bullet atom in the drug development: perspective to FDA approved and COVID-19 recommended drugs

“…3b) repel each other at gauche conformation, and in this case, staggered conformation dominates (Fig. 3b) (Dong and Tsui 2021).…”

“…Traditionally, we introduce fluorine atom/s by electrophilic or nucleophilic reagents and a good number of reagents have been developed (Caron 2020). In the last ten years, a growth of interest has been seen in the development of methods of fluorination through thermal (Nonn et al 2022;Dong and Tsui 2021;Campbell and Ritter 2014) or photochemical radical reactions (Sibi and Landais 2013;Kindt and Heinrich 2014;Li et al 2013;Cui et al 2016;Meyer et al 2018). We have now good methods of regio-and enantioselective introduction of a fluorine atom or fluorine-containing substituent in organic compounds.…”

Solution and solid-state studies of hydrogen and halogen bonding with N-heterocyclic carbene supported nickel(ii) fluoride complexes

“…Late transition metal fluoride complexes are discussed as key species for stoichiometric and catalytic C–F bond activation 18 and formation. 19 In the field of C–F activation, oxidative addition of a fluorinated organic compound at a low-valent metal centre such as Ni(0) occurs readily and this reaction has been studied experimentally and computationally for a wide range of bis(phosphine) group 10 complexes. 20 Similar reactions of bis(NHC) (NHC = N-heterocyclic carbene) complexes were studied later, using readily accessible Ni(NHC) 2 precursors such as the cyclooctadiene bridged dimer (NHC) 2 Ni(μ-C 8 H 12 )Ni(NHC) 2 , the ethylene complex (NHC) 2 Ni(η 2 -C 2 H 4 ), or Ni(NHC) 2 (Scheme 1).…”