Visible-light-mediated C–F bond cleavage for the synthesis of polyfluorinated compounds

Abstract

Herein, we describe a novel and efficient photo-redox catalytic difluorinated ester radical addition/defluoroalkylation coupling reaction between trifluoroacetic acid derivatives and α-trifluoromethyl alkenes. A series of polyfluorinated compounds were synthesized by...

Recent Advance in the C−F Bond Functionalization of Trifluoromethyl Aromatic and Carbonyl Compounds

“…In 2023, Liang and Liu reported the visible-light-induced allylic defluorinative cross-coupling reaction using trifluoroacetic acid derivatives and α-trifluoromethyl alkenes (Scheme 8VI). [30] Through the SCS and SET pathways, a range of polyfluorinated compounds were successfully synthesized, demonstrating excellent tolerance towards various functional groups. The mechanism proposed that the CO 2 *À played a pivotal role as a potent reductant in the formation of crucial radical intermediates.…”

Recent Advances in Reactions Involving Carbon Dioxide Radical Anion

“…•− as the reductant to realize the difluorinated ester radical addition/defluoroalkylation process to access polyfluorinated compounds (Scheme 10). 26 •− to furnish difluorinated ester radical 5a. Subsequent radical addition to 25a produced 27, which underwent SET to formed benzyl anion 28.…”

“…Recently, Liang and co-workers further utilized the photoredox/HAT strategy with CO 2 •– as the reductant to realize the difluorinated ester radical addition/defluoroalkylation process to access polyfluorinated compounds (Scheme ). This reaction features mild reaction conditions and good functional group compatibility. A tentative reaction mechanism is outlined in Scheme .…”

Visible-Light-Induced Defluorinative α-C(sp3)–H Alkylation for the Synthesis of gem-Difluoroallylated α-Trifluoromethylamines

“…Fluoroalkenes, especially gem -difluoroalkenes, are known not only as a bioisostere of carbonyl compounds for applications in pharmaceuticals and drugs due to their metabolic stability and bioactivity but also as a versatile synthetic building block for the synthesis of other fluorine-containing structures in organic synthesis (Figure b). , In recent years, photoredox-catalyzed and transition-metal-catalyzed (Pd, Ni, Ti, Zn, Cr) defluorinative cross-coupling reactions of α-trifluoromethyl alkenes with various electrophiles or radical precursors offer an approach to construct diverse gem -difluoroalkenes through a radical to polar crossover mechanism (Scheme b). The incorporation of two bioactive moieties into another unique and complex structure is an important strategy in medicinal chemistry for providing new compound libraries for bioassays.…”