1365122-33-3

Upstream product

• 621-23-8 1,2,3-trimethoxybenzene 
• 2926-29-6 Langlois reagent 
• 56572-25-9 2-(trifluoromethylsulfonyl)-N-tert-butoxycarbonylhydrazine 
• 421-83-0 trifluoromethane sulfonyl chloride 
• 75-63-8 Bromotrifluoromethane 
• 2926-30-9 sodium triflate 
• 887144-97-0 Togni's reagent 
• 1961266-44-3 2,8-difluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium trifluoromethanesulfonate 
• 887144-94-7 Togni's reagent II 
• 1422738-67-7 sodium 1,1-difluoroethane-1-sulfinate 
• 1374745-98-8 1-(naphthalen-2-yl)-2-((trifluoromethyl)sulfonyl)ethan-1-one 
• 35896-48-1 1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one 
• 98821-06-8 (1-Trifluoromethanesulfonyl-ethyl)-benzene 
• 36750-88-6 1-phenyl-3,3,3-trifluoro-1,2-propanedione 

Relevant academic research and scientific papers

Photoorganocatalysed and visible light photoredox catalysed trifluoromethylation of olefins and (hetero)aromatics in batch and continuous flow

Trifluoromethylation of olefins and (hetero)aromatics with sodium triflinate as CF3 source and readily accessible benzophenone derivatives as photosensitisers has been developed in batch and flow. The use of an iridium-based photocatalyst enables the trifluoromethylation to proceed under visible light irradiation.

Nickel(IV)-Catalyzed C-H Trifluoromethylation of (Hetero)arenes

This Article describes the development of a stable NiIV complex that mediates C(sp2)-H trifluoromethylation reactions. This reactivity is first demonstrated stoichiometrically and then successfully translated to a NiIV-catalyzed C-H trifluoromethylation of electron-rich arene and heteroarene substrates. Both experimental and computational mechanistic studies support a radical chain pathway involving NiIV, NiIII, and NiII intermediates.

Delayed fluorescence from a zirconium(iv) photosensitizer with ligand-to-metal charge-transfer excited states

Advances in chemical control of the photophysical properties of transition-metal complexes are revolutionizing a wide range of technologies, particularly photocatalysis and light-emitting diodes, but they rely heavily on molecules containing precious metals such as ruthenium and iridium. Although the application of earth-abundant ‘early’ transition metals in photosensitizers is clearly advantageous, a detailed understanding of excited states with ligand-to-metal charge transfer (LMCT) character is paramount to account for their distinct electron configurations. Here we report an air- and moisture-stable, visible light-absorbing Zr(iv) photosensitizer, Zr(MesPDPPh)2, where [MesPDPPh]2? is the doubly deprotonated form of [2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine]. This molecule has an exceptionally long-lived triplet LMCT excited state (τ = 350 μs), featuring highly efficient photoluminescence emission (Ф = 0.45) due to thermally activated delayed fluorescence emanating from the higher-lying singlet configuration with significant LMCT contributions. Zr(MesPDPPh)2 engages in numerous photoredox catalytic processes and triplet energy transfer. Our investigation provides a blueprint for future photosensitizer development featuring early transition metals and excited states with significant LMCT contributions. [Figure not available: see fulltext.]

Sunlight decatungstate photoinduced trifluoromethylations of (hetero)aromatics and electron-poor olefins

Tetrabutylammonium decatungstate has been exploited to photoinduce the trifluoromethylation of (hetero)aromatics and electron-poor olefins. The process made use of the cheap Langlois' reagent (CF3SO2Na) and occurred under sunlight irradiation in an acetonitrile/water mixture. The trifluoromethylation of (hetero)aromatics required the use of potassium persulfate as an additive and the mono- or bis-trifluoromethylated adducts were obtained, depending on the actual reaction conditions and the chosen substrate.

Development of a Quinolinium/Cobaloxime Dual Photocatalytic System for Oxidative C-C Cross-Couplings via H2Release

Designing molecular photocatalysts for potent photochemical reactivities ranks among the most challenging but rewarding endeavors in synthetic photochemistry. Herein, we document a quinoline-based organophotoredox catalyst, 2,4-bis(4-methoxyphenyl)quinoli

Rational Design and Development of Low-Price, Scalable, Shelf-Stable and Broadly Applicable Electrophilic Sulfonium Ylide-Based Trifluoromethylating Reagents

The development of two highly reactive electrophilic trifluoromethylating reagents (trifluoromethyl)(4-nitrophenyl)bis(carbomethoxy)methylide (1g) and (trifluoromethyl)(3-chlorophenyl)bis(carbomethoxy)methylide (1j) through structure-activity study was described. Under mild conditions, reagent 1g reacted with β-ketoesters and silyl enol ethers to give α-trifluoromethylated-β-ketoesters or α-trifluoromethylated ketones in high yields. In addition, reagent 1g could serve as a trifluoromethyl radical for a variety of trifluoromethylative transformations under visible light irradiation, including radical trifluoromethylation of electron-rich indoles and pyrroles and sodium aryl sulfinates as well as trifluoromethylative difunctionalization with styrene derivatives. On the other hand, as a complimentary, under reductive coupling conditions, reagent 1j reacted with a variety of (hetero)aryl iodides for the formation of trifluoromethylated (hetero)arenes.

Exploring the Structure and Performance of Cd–Chalcogenide Photocatalysts in Selective Trifluoromethylation

The field of heterogeneous photoredox catalysis has grown substantially and impacted organic synthesis because of the affordability and reusability of catalysts. This study reports radical trifluoromethylation with Cd–chalcogenide semiconductors. Cd semiconductors, particularly CdSe, are readily available, commercial, visible-light-responsive, heterogeneous photocatalysts. The potential of readily available Cd semiconductors, particularly CdSe, is confirmed by their increased photocatalytic activity toward trifluoromethylation with various substrates, such as (hetero)arenes and vinylic amides/acids, via addition, cyclization, and decarboxylation under visible light. The economic significance of this strategy is also highlighted through the scalable synthesis of biologically active molecules followed by catalyst reuse. Moreover, these catalysts are relatively inexpensive compared with transition metal-based homogeneous photocatalysts, presently used in organic synthesis.

Solvated Nickel Complexes as Stoichiometric and Catalytic Perfluoroalkylation Agents**

The acetonitrile-solvated [(MeCN)Ni(C2F5)3]? was prepared in order to compare and contrast its reactivity with the known [(MeCN)Ni(CF3)3]? towards organic electrophiles. Both [(MeCN)Ni(CF3)3]? and [(MeCN)Ni(C2F5)3]? successfully react with aryl iodonium and diazonium salts as well as alkynyl iodonium salts to give fluoroalkylated organic products. Electrochemical analysis of [(MeCN)NiII(C2F5)3]? suggests that, upon electro-oxidation to [(MeCN)nNiIII(C2F5)3], reductive homolysis of a perfluoroethyl radical occurs, with the concomitant formation of [(MeCN)2NiII(C2F5)2]. Catalytic C?H trifluoromethylations of electron-rich arenes were successfully achieved using either [(MeCN)Ni(CF3)3]? or the related [Ni(CF3)4]2?. Stoichiometric reactions of the solvated nickel complexes reveal that “ligandless” nickel is exceptionally capable of serving as reservoir of CF3 groups under catalytically relevant conditions.

Versatile Open-Source Photoreactor Architecture for Photocatalysis across the Visible Spectrum

Adoption of commercial photoreactors as standards for photocatalysis research could be limited by high cost. We report the development of the Wisconsin Photoreactor Platform (WPP), an open-source photoreactor architecture potentially suitable for general

Photoinduced Trifluoromethylation of Arenes and Heteroarenes Catalyzed by High-Valent Nickel Complexes

We describe a series of air-stable NiIII complexes supported by a simple, robust naphthyridine-based ligand. Access to the high-valent oxidation state is enabled by the CF3 ligands on the nickel, while the naphthyridine exhibits either a monodentate or bidentate coordination mode that depends on the oxidation state and sterics, and enables facile aerobic oxidation of NiII to NiIII. These NiIII complexes act as efficient catalysts for photoinduced C(sp2)?H bond trifluoromethylation reactions of (hetero)arenes using versatile synthetic protocols. This blue LED light-mediated catalytic protocol proceeds via a radical pathway and demonstrates potential in the late-stage functionalization of drug analogs.