Einführung von Fluor und fluorhaltigen funktionellen Gruppen

Abstract

Die wichtigsten konzeptionellen Fortschritt auf dem Gebiet der Fluorierungen der letzten zehn Jahre wurden durch die Organo‐ und Übergangsmetallkatalyse ermöglicht. 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 Allgemeingültigkeit, Vorhersagbarkeit und Kosteneffizienz. Trotz der Einschränkungen sind fluorierte Verbindungen mit modernen Fluorierungsmethoden leichter zugänglich als je zuvor. Vor allem beginnen sich die modernen Methoden auf Forschungsgebiete auszuwirken, die keine großen Materialmengen benötigen, z. B. die Wirkstoffentwicklung und die Positronenemissionstomographie. Diese Entwicklungen werden in diesem Aufsatz zusammengefasst und vor dem Hintergrund konventioneller Fluorierungsmethoden diskutiert.

Hydrotrifluoromethylthiolation of Unactivated Alkenes and Alkynes with Trifluoromethanesulfonic Anhydride through Deoxygenative Reduction and Photoredox Radical Processes

“…[1] Recently,n umerous methods have been developed for the incorporation of an SCF 3 group into organic skeletons. [2] The rapid progress in this area has mostly been due to the invention of as eries of easy-to-handle electrophilic trifluoromethylthiolating reagents. [3] These reagents include R 2 N-SCF 3 reagents (trifluoromethanesulfenamide, N-SCF 3 -succinimide, N-SCF 3 -phthalimide, N-SCF 3 -saccharin), [4] RO-SCF 3 reagents (trifluoromethanesulfenates), [5] and RSO 2 CF 3 reagents (CF 3 SO 2 -containing hypervalent iodonium ylide or diazo compounds, [6] CF 3 SO 2 Na, [7] CF 3 SO 2 Cl, [8] and CF 3 SO 2 NHNHBoc [9] ).…”

From QCA (Quantum Cellular Automata) to Organocatalytic Reactions with Stabilized Carbenium Ions

“…Benzodithiol can be also used as a synthetic equivalent of the CO and CF 2 groups,103 as we have recently shown (Scheme ). Using this straightforward methodology, it is possible to install the CF 2 unit near stereogenic centers for the synthesis of complex difluorinated molecules 104…”

“…Using this straightforward methodology, it is possible to install the CF 2 unit near stereogenic centers for the synthesis of complex difluorinated molecules. [104] It is also quite remarkable that the benzodithiol group can be easily removed by treatment of the protected derivative obtained after alkylation by Raney-nickel V R . Thus, the benzodithiol introduced by an organocatalytic reaction is a methyl equivalent.…”

Nickel‐Catalyzed Carbofluoroalkylation of 1,3‐Enynes to Access Structurally Diverse Fluoroalkylated Allenes

“…[3] To provide collections of fluorinated molecules having skeletal and stereochemical diversity,the development of efficient methods for facile synthesis of diverse fluorinated allenes could therefore meet the great demand of drug discovery and new materials development. [5] As ar esult, the design and synthesis of novel fluorinating and fluoroalkylating building blocks has been considered as one of the most powerful approaches to realize diverse fluorination and fluoroalkylation, respectively, of organic molecules. [5] As ar esult, the design and synthesis of novel fluorinating and fluoroalkylating building blocks has been considered as one of the most powerful approaches to realize diverse fluorination and fluoroalkylation, respectively, of organic molecules.…”