Fluorinated Rings: Conformation and Application

Abstract

The introduction of fluorine atoms into molecules and materials across many fields of academic and industrial research is now commonplace, owing to their unique properties. A particularly interesting feature is the impact of fluorine substitution on the relative orientation of a C−F bond when incorporated into organic molecules. In this Review, we will be discussing the conformational behavior of fluorinated aliphatic carbo‐ and heterocyclic systems. The conformational preference of each system is associated with various interactions introduced by fluorine substitution such as charge‐dipole, dipole‐dipole, and hyperconjugative interactions. The contribution of each interaction on the stabilization of the fluorinated alicyclic system, which manifests itself in low conformations, will be discussed in detail. The novelty of this feature will be demonstrated by presenting the most recent applications.

Enantio‐ and Diastereoselective, Complete Hydrogenation of Benzofurans by Cascade Catalysis

“…[17] Fluorinated, saturated carbocycles are emerging motifs in drug discovery and the design of functional materials. [18] This class of compounds attracts increasing attention, since incorporating fluoro moieties into target molecules allows for the modulation of their physicochemical properties with little influence on steric demand. [19] Although hydrogenation…”

Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis

“… 51 These materials, together with selectively fluorinated tetralins ( 30 ), 52 hold great potential as drug discovery modules owing to their well-defined conformations and physicochemical profiles. 53 …”

Recent Developments in Enantioselective Organocatalytic Cascade Reactions for the Construction of Halogenated Ring Systems

“…A few enantioselective halolactonizations were described, besides some racemic cascade processes. In 2021 Nairoukh and coworkers revised the literature on fluorinated rings focusing in particular their conformational behavior and the impact of the fluorine orientation on structure, shape and the physical and thermodynamic properties of the fluorine‐containing materials, including its effect on pharmaceuticals, catalysis and organic synthesis [35] . Additional references relative to each type of halogenation reaction are included in the respective sections below.…”

“…[27][28][29][30][31] The literature on reactions leading to compounds bearing chiral halogen-containing centers has been reviewed periodically. [32][33][34][35] In 2020 Li and coworkers surveyed the literature available on methods for the asymmetric construction of cyclic molecules, involving both organocatalysis and metalcatalyzed processes, but concentrated exclusively on those containing a halogenated tetrasubstituted stereocenter, [34a] while China, Dohi and coworkers surveyed in the same year cyclization reactions, asymmetric or not, induced by a halogen. [34b] A few enantioselective halolactonizations were described, besides some racemic cascade processes.…”