4707-12-4

Upstream product

• 652-18-6 2,3,5,6-tetrafluorobenzoic acid 
• 67-56-1 methanol 
• 115-18-4 2-methyl-3-buten-2-ol 
• 36629-42-2 methyl pentafluorobenzoate 
• 65781-16-0 1,2,3,4,5-pentafluoro-6-((2-methylbut-3-en-2-yl)oxy)benzene 
• 24509-88-4 2-methyl-3-buten-2-yl acetate 
• 1040738-23-5 2-fluoro-6-((2-methylbut-3-en-2-yl)oxy)pyridine 
• 727-55-9 dimethyl 2,3,5,6-tetrafluoroterephthalate 
• 602-94-8 Pentafluorobenzoic acid 

Downstream Products

• 1003295-27-9 3-azido-1,2,4,5-tetrafluorobenzene 

Relevant academic research and scientific papers

Diazaphospholene-Catalyzed Hydrodefluorination of Polyfluoroarenes with Phenylsilane via Concerted Nucleophilic Aromatic Substitution

The metal-free catalytic C-F bond activation of polyfluoroarenes was achieved with diazaphospholene as the catalyst and phenylsilane as the terminal reductant. Density functional theory calculations suggested a concerted nucleophilic aromatic substitution mechanism.

Photoredox catalysis on unactivated substrates with strongly reducing iridium photosensitizers

Photoredox catalysis has emerged as a powerful strategy in synthetic organic chemistry, but substrates that are difficult to reduce either require complex reaction conditions or are not amenable at all to photoredox transformations. In this work, we show that strong bis-cyclometalated iridium photoreductants with electron-rich β-diketiminate (NacNac) ancillary ligands enable high-yielding photoredox transformations of challenging substrates with very simple reaction conditions that require only a single sacrificial reagent. Using blue or green visible-light activation we demonstrate a variety of reactions, which include hydrodehalogenation, cyclization, intramolecular radical addition, and prenylationviaradical-mediated pathways, with optimized conditions that only require the photocatalyst and a sacrificial reductant/hydrogen atom donor. Many of these reactions involve organobromide and organochloride substrates which in the past have had limited utility in photoredox catalysis. This work paves the way for the continued expansion of the substrate scope in photoredox catalysis.

Catalyst-Free Hydrodefluorination of Perfluoroarenes with NaBH4

Presented is an economical means of removing fluorine from various highly fluorinated arenes using NaBH4. The procedure was adapted for different classes of perfluoroarenes. A novel isomer of an emerging class of organic dyes based on the carbazole phthalonitrile motif was succinctly synthesized in two steps from tetrafluorophthalonitrile, demonstrating the utility of the hydrodefluorination procedure. Initial exploration of the dye shows it to be photoactive and capable of facilitating contrathermodynamic styrenoid E/Z isomerization.

Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers

Herein, we report a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, Phebox-Bi(I) and OMe-Phebox-Bi(I). Mechanistic studies on the elementary steps support a Bi(I)/Bi(III) redox cycle that comprises C(sp2)-F oxidative addition, F/H ligand metathesis, and C(sp2)-H reductive elimination. Isolation and characterization of a cationic Phebox-Bi(III)(4-tetrafluoropyridyl) triflate manifests the feasible oxidative addition of Phebox-Bi(I) into the C(sp2)-F bond. Spectroscopic evidence was provided for the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to afford the corresponding C(sp2)-H bond while regenerating the propagating Phebox-Bi(I). This protocol represents a distinct catalytic example where a main-group center performs three elementary organometallic steps in a low-valent redox manifold.

Microwave-Assisted Synthesis and Molecular Docking Studies of Fluorinated 1,3,4-Oxadiazole Derivatives as Antimicrobial Agent

Abstract: A series of phenyl-5-(2,3,5,6-tetrafluoro-phenyl)-[1,3,4]-oxadiazole were prepared from 2,3,5,6-tetrafluoro-benzoic acid hydrazide by treatment with various substituted benzoic acid in the presence of phosphorus oxychloride using conventional as well as microwave-assisted methods. Evaluation of antibacterial activity of synthesized compound against S. aures, S. pyogenes, S. typhi and Pseudomonas species and antifungal activity against C. albicans and A. niger has been carried out. The compounds (Vb) and (Ve) showed significant activity against both bacteria and fungi. Some of the compounds has shown moderate activity against both the bacteria and fungi. The molecular docking studies also done which support the antimicrobial activity exhibited high inhibition constant and binding energy. The chemical structures of all the synthesized compounds were elucidated by their IR, 1H NMR and mass spectra.

Hydrogen Bond Directed Photocatalytic Hydrodefluorination and Methods of Use Thereof

Methods of synthesizing compounds comprising fluorinated aryl groups are disclosed, wherein said methods utilize hydrogen bond directed photocatalytic hydrodefluorination.

Prenyl Praxis: A Method for Direct Photocatalytic Defluoroprenylation

The prenyl fragment is the quintessential constituent of terpenoid natural products, a diverse family which contains numerous members with diverse biological properties. In contrast, fluorinated and multifluorinated arenes make up an important class of anthropogenic molecules which are highly relevant to material, agricultural, and pharmaceutical industries. While allylation chemistry is well developed, effective prenylation strategies have been less forthcoming. Herein, we describe the photocatalytic defluoroprenylation, a powerful method that provides access to "hybrid molecules" that possess both the functionality of a prenyl group and fluorinated arenes. This approach involves direct prenyl group transfer under very mild conditions, displays excellent functional group tolerance, and includes relatively short reaction times (4 h), which is the fastest photocatalytic C-F functionalization developed to date. Additionally, the strategy can be extended to include allyl and geranyl (10 carbon fragment) transfers. Another prominent finding is a reagent-dependent switch in regioselectivity of the major product from para to ortho C-F functionalization.

Identifying the potential of pulsed LED irradiation in synthesis: Copper-photocatalysed C-F functionalisation

It has been reported that pulsed irradiation can improve photosynthetic activity and phytochemical production in plants. Intrigued and inspired by these observations, we postulated that pulsed irradiation strategies may have broader implications in organic synthesis. We report here the results of a proof-of-concept study demonstrating that pulsed LED irradiation enhances the efficiency of a visible light-mediated photoredox-catalysed reaction. The design and construction of an inexpensive multiphase circuit (～US$5) enabling power and pulse frequency modulation, which is connected to light-emitting diodes (LEDs), provides a source of pulsed visible light. This technology was then utilised to establish a novel copper-photocatalysed dual α-amino C-H/C-F functionalisation reaction. Pulsed blue LED irradiation was shown to be crucial for facilitating a much more efficient process and increasing the rate of product formation. Our results suggest that pulsed irradiation strategies have the potential to contribute to enhancing the synthetic utility and extending the scope of first row transition metal-based photoredox catalysts. We also anticipate that this approach will find wider applications in synthesis.

Transition-Metal-Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate

A transition-metal-free catalytic hydrodefluorination (HDF) reaction of polyfluoroarenes is described. The reaction involves direct hydride transfer from a hydrosilicate as the key intermediate, which is generated from a hydrosilane and a fluoride salt. The eliminated fluoride regenerates the hydrosilicate to complete the catalytic cycle. Dispersion-corrected DFT calculations indicated that the HDF reaction proceeds through a concerted nucleophilic aromatic substitution (CSNAr) process.

Hydrodefluorination of Fluoroarenes Using Hydrogen Transfer Catalysts with a Bifunctional Iridium/NH Moiety

The hydrodefluorination of fluoroarenes with transfer hydrogenation catalysts using 2-propanol or potassium formate is described. With the aid of metal/NH cooperation, the C-N chelating Ir complexes derived from benzylic amines can efficiently promote the reduction involving the C-F bond cleavage under ambient conditions even in the absence of hydrosilanes or H2 gas, leading to the partially fluorinated products in good yields and with high selectivity.