Photocatalytic Monofluorination of Benzene by Fluoride via Photoinduced Electron Transfer with 3-Cyano-1-methylquinolinium

Abstract

The photocatalytic fluorination of benzene occurs under photoirradiation of an oxygen-saturated acetonitrile (MeCN) of the 3-cyano-1-methylquinolinium ion (QuCN(+)) containing benzene and tetraethylammonium fluoride tetrahydrofluoride (TEAF·4HF) with a xenon lamp (500 W) attached to a colored-glass filter (λ < 290 nm) to yield fluorobenzene and hydrogen peroxide. The quantum yield of formation of fluorobenzene was 6%. Nanosecond laser flash photolysis measurements were performed to elucidate the mechanistic details for photocatalytic fluorination. Transient absorption spectra taken after the nanosecond laser excitation at 355 nm of a degassed MeCN solution of QuCN(+) and benzene exhibited absorption bands due to QuCN(•) (λmax = 500 nm) and the benzene dimer radical cation (λmax = 900 nm), which were generated by photoinduced electron transfer from benzene to the singlet excited state of QuCN(+). The decay rate of the transient absorption band due to the benzene dimer radical cation was accelerated by the addition of TEAF·4HF. The observed rate constant increased with increasing concentration of TEAF·4HF. The rate constant of the electrophilic addition of fluoride to the benzene radical cation was determined to be 9.4 × 10(9) M(-1) s(-1). Thus, the photocatalytic reaction is initiated by intermolecular photoinduced electron transfer from benzene to the single excited state of QuCN(+). The benzene radical cation formed by photoinduced electron transfer reacts with the fluoride anion to yield the F-adducted radical. However, QuCN(•) can reduce O2 to O2(•-), and this is followed by the protonation of O2(•-) to afford HO2(•). The hydrogen abstraction of HO2(•) from the F-adduct radical affords fluorobenzene and H2O2 as the final products.

X-ray–driven reaction front dynamics at calcite-water interfaces

“…www.sciencemag.org/content/349/6254/1330/suppl/DC1 Materials and Methods Figs. S1 to S9 Tables S1 and S2 References (22)(23)(24)(25)(26)(27)(28)(29)(30)(31)(32)(33)(34)(35)(36)(37) Movies S1 to S6 (compressed video files)…”

Ultrafast Observation of a Photoredox Reaction Mechanism: Photoinitiation in Organocatalyzed Atom-Transfer Radical Polymerization

“…[11][12][13] They have also been used in the photocatalytic reduction of carbon dioxide to methane 14 and in the development of cooperative catalysis. [15][16][17][18][19][20][21][22] To circumvent the problems of natural scarcity and toxicity associated with the transition metals in these photoredox systems, [23][24] researchers are replacing metal-based catalysts with highly conjugated organocatalysts; [25][26][27] applications, and associated mechanistic studies, include oxidation using molecular oxygen, [28][29][30] cross-coupling, 31 cyanation, 32 addition to alkenes, 33 trifluoromethylation, 34 hydroxylation, 35 N-formylation, 36 and sulfinylation. 37 In addition to these synthetic uses, selected organic PCs such as perylene, phenothiazine, dihydrophenazine and phenoxazine derivatives have recently been applied in the development of organocatalysed atom-transfer radical polymerization (O-ATRP).…”

Organic synthetic transformations using organic dyes as photoredox catalysts

“…67 The yield of fluorobenzene after 50 min of photoirradiation was 20% with 40% conversion of benzene. 67 Phenol was also detected as a side-product through the photocatalytic oxygenation of benzene with QuCN + in the presence of a small amount of H 2 O containing MeCN (vide supra). When benzene was replaced with fluorobenzene as the substrate, no fluorination occurred to yield difluorobenzene.…”