Organocatalyzed Fluoride Metathesis

Abstract

A new organocatalyzed fluoride metathesis reaction between fluoroarenes and carbonyl derivatives is reported. The reaction exchanges fluoride (F − ) and alternate nucleophiles (OAc − , OCO 2 R − , SR − , Cl − , CN − , NCS − ). The approach provides a conceptually novel route to manipulate the fluorine content of organic molecules. When the fluorination and defluorination steps are combined into a single catalytic cycle, a byproduct free and 100% atom-efficient reaction can be achieved.

Au(I) Catalyzed HF Transfer: Tandem Alkyne Hydrofluorination and Perfluoroarene Functionalisation

“…Multiple SNAr reactions are expected and are consistent with previous reports for these fluoroarenes. 34,35 The reaction could also be applied to both alkyl and aryl internal alkynes allowing the formation of 2b-d as products of HF transfer. In every case, the hydrofluorination was 100 % trans-selective.…”

Studies on the Synthesis of Perfluoroaryl Sulfides and their Application in Desulfurative Nickel-Catalyzed Reductive Cross-Coupling

“…In particular, the development of methods to introduce sulfur selectively into polyfluoroarenes is of growing importance, as polyfluoroaromatic sulfur-containing compounds are often encountered in pharmaceuticals (Scheme 1B), agrochemicals, and functional materials. [37][38][39][40] While recent developments have made polyfluoroaryl-sulfides synthetically accessible, [41][42][43][44][45][46][47] some reported synthetic processes still suffer from limitations, including poor regioselectivity. [41][42][43][44] Other strategies are rather complex and require the preparation of hetarenium salts for the synthesis.…”

“…[37][38][39][40] While recent developments have made polyfluoroaryl-sulfides synthetically accessible, [41][42][43][44][45][46][47] some reported synthetic processes still suffer from limitations, including poor regioselectivity. [41][42][43][44] Other strategies are rather complex and require the preparation of hetarenium salts for the synthesis. [43][44] There are also other methods that have only been used in very focused settings, such as the preparation of polymers 45 and peptide stapling.…”

“…[41][42][43][44] Other strategies are rather complex and require the preparation of hetarenium salts for the synthesis. [43][44] There are also other methods that have only been used in very focused settings, such as the preparation of polymers 45 and peptide stapling. [46][47] To deal with these issues, we attempted to develop a metal-free defluorosulfurization method for the synthesis of perfluoroarenes using SNAr chemistry, with a focus on the following considerations: 1) highly selective substitution of C−F bonds by mercaptans or thiolates; and 2) broad applicability with high functional group tolerance, making it suitable for the modification of complex molecules.…”

Carboxylic Acid Deoxyfluorination and One-Pot Amide Bond Formation Using Pentafluoropyridine (PFP)

“…In this regard, it is worth noting that Crimmin has successfully generated acyl fluorides in the reaction of acetic anhydrides with PFP and DMAP. 16 However, in this reaction sequence, addition of DMAP is required and acyl fluoride generation was not the primary focus of the work. PFP ( 2 ) also shares some structural similarities with other deoxyfluorination reagents, for example, cyuranic fluoride.…”