Over the past decade, the most significant, conceptual advances in the field of fluorination were enabled most prominently by organo- and transition-metal catalysis. The most challenging transformation remains the formation of the parent C-F bond, primarily as a consequence of the high hydration energy of fluoride, strong metal-fluorine bonds, and highly polarized bonds to fluorine. Most fluorination reactions still lack generality, predictability, and cost-efficiency. Despite all current limitations, modern fluorination methods have made fluorinated molecules more readily available than ever before and have begun to have an impact on research areas that do not require large amounts of material, such as drug discovery and positron emission tomography. This Review gives a brief summary of conventional fluorination reactions, including those reactions that introduce fluorinated functional groups, and focuses on modern developments in the field.

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Introduction of Fluorine and Fluorine-Containing Functional Groups

Successful fluorine-containing herbicide agrochemicals

Die wichtigsten konzeptionellen Fortschritt auf dem Gebiet der Fluorierungen der letzten zehn Jahre wurden durch die Organo- und Ubergangsmetallkatalyse ermoglicht. Die schwierigste Umwandlung ist weiterhin die Bildung der C-F-Stammbindung, was in erster Linie eine Folge der hohen Hydratationsenergie von Fluorid, starker Metall-Fluor-Bindungen und der hoch polarisierten Bindungen zu Fluor ist. Den meisten Fluorierungen fehlt es immer noch an Allgemeingultigkeit, Vorhersagbarkeit und Kosteneffizienz. Trotz der Einschrankungen sind fluorierte Verbindungen mit modernen Fluorierungsmethoden leichter zuganglich als je zuvor. Vor allem beginnen sich die modernen Methoden auf Forschungsgebiete auszuwirken, die keine grosen Materialmengen benotigen, z. B. die Wirkstoffentwicklung und die Positronenemissionstomographie. Diese Entwicklungen werden in diesem Aufsatz zusammengefasst und vor dem Hintergrund konventioneller Fluorierungsmethoden diskutiert.

Einführung von Fluor und fluorhaltigen funktionellen Gruppen

In the last few years, transition metal-mediated reactions have joined the toolbox of chemists working in the field of fluorination for Life-Science oriented research. The successful execution of transition metal-catalyzed carbon–fluorine bond formation has become a landmark achievement in fluorine chemistry. This rapidly growing research field has been the subject of some excellent reviews. Our approach focuses exclusively on transition metal-catalyzed reactions that allow the introduction of –CFH2, –CF2H, –CnF2n+1 and –SCF3 groups onto sp² carbon atoms. Transformations are discussed according to the reaction-type and the metal employed. The review will not extend to conventional non-transition metal methods to these fluorinated groups.

https://www.beilstein-journals.org/bjoc/content/pdf/1860-5397-9-287.pdf

Recent advances in transition metal-catalyzed Csp 2 -monofluoro-, difluoro-, perfluoromethylation and trifluoromethylthiolation

Because of the unique properties of the trifluoromethoxy group, molecules bearing this moiety will find applications in various fields, particularly in the life sciences. However, despite the great interest in this functional group, only a small number of trifluoromethoxylated molecules are currently synthetically accessible. Over the last few years, several innovative and promising strategies for the synthesis of trifluoromethoxylated compounds have been described. This Minireview discusses these existing methods with a particular focus on more recent advances.

Synthetic Approaches to Trifluoromethoxy-Substituted Compounds.

Synthesis of diversely fluorinated pyrazoles as novel active agrochemical ingredients

A General Approach to (Trifluoromethoxy)pyridines: First X-ray Structure Determinations and Quantum Chemistry Studies

A New Life for an Old Reagent: Fluoroalkyl Amino Reagents as Efficient Tools for the Synthesis of Diversely Fluorinated Pyrazoles†

A New Synthesis and Process Development of Bis(fluoroalkyl)pyrazoles As Novel Agrophores

Fluorine, the most electronegative element plays nowadays a key role in pharmaceutical, agrochemical and material sciences. It has been estimated that the number of fluorinated compounds currently under development represents some 30–50% of the total active ingredients in development. The search for new active substances with improved efficacy, lower mammalian toxicity, more favourable environmental profile and lower cost is a truly challenging task for R&D chemists within the crop protection companies. The present review will give an overview on the synthesis of pyrazoles bearing novel fluorinated substituents.

Florence Giornal

Papers

Synthesis of diversely fluorinated pyrazoles as novel active agrochemical ingredients

A General Approach to (Trifluoromethoxy)pyridines: First X-ray Structure Determinations and Quantum Chemistry Studies

A New Life for an Old Reagent: Fluoroalkyl Amino Reagents as Efficient Tools for the Synthesis of Diversely Fluorinated Pyrazoles†

A New Synthesis and Process Development of Bis(fluoroalkyl)pyrazoles As Novel Agrophores

Synthesis of Diversely Fluorinated Pyrazoles as Novel Active Agrochemical Ingredients