Palladium-Catalyzed Intermolecular Aminofluorination of Styrenes

Abstract

A novel palladium-catalyzed intermolecular aminofluorination of styrenes, with N-fluorobenzenesulfonimide (NFSI) functioning not only as a fluorinating reagent but also as an aminating reagent, has been developed. The reaction afforded vicinal fluoroamine products with very high regioselectivity. This transformation may involve fluoropalladation of styrene as a key step for C-F bond formation. The bidental nitrogen ligand is crucial to achieving the transformation successfully.

Palladium-catalyzed inter- and intramolecular hydroamination of styrenes coupled with alcohol oxidation using N-fluorobenzenesulfonimide as the oxidant

“…The ligand screening results showed that bathocuproine is better than the others (entries 6, 11e12). It is worthy noted that the aminofluorination product was obtained in the absence of alcohol [16].…”

Transition Metal-Mediated and Metal-Catalyzed Carbon–Fluorine Bond Formation

“…An application of palladium-catalyzed electrophilic fluorination was reported by Liu and coworkers in 2010 [50]. Imidofluorination of styrenes with NFBS occurred regioselectively (Fig.…”

Catalytic Aminohalogenation of Alkenes and Alkynes

“…25 (1) Liu and co-workers disclosed a regioselective Pd-catalyzed intermolecular aminofluorination of styrenes in 2010 using NFSI as the fluorine source and stoichiometric (2.5 equiv) oxidant (Scheme 21). 26 The regioselectivity is analogous to a Markovnikov electrophile-initiated haloamination. The authors proposed a mechanism involving fluoropalladation and subsequent C-N bond formation from the organopalladium intermediate.…”