120120-40-3

Upstream product

• 75-63-8 Bromotrifluoromethane 
• 135285-01-7 2,6-Di-tert-butyl-phenolatetetramethyl-ammonium; 
• 2314-97-8 iodotrifluoromethane 
• 7175-96-4 2,6-di-tert-butylphenolate, sodium salt 
• 120120-30-1 2,6-di-tert-butyl-4-(triethylsiloxy)-4-(trifluoromethyl)-2,5-cyclohexadien-1-one 
• 7487-94-7 mercury (II) chloride 
• 887144-94-7 Togni's reagent II 
• 128-39-2 2,6-di-tert-butylphenol 
• 2926-29-6 Langlois reagent 
• 1961266-44-3 2,8-difluoro-5-(trifluoromethyl)-5H-dibenzo[b,d]thiophen-5-ium trifluoromethanesulfonate 
• 2926-30-9 sodium triflate 

Relevant academic research and scientific papers

Metal- and oxidant-free photoinduced aromatic trifluoromethylation performed in aerated gel media: Determining the effects on yield and selectivity

In this work we have investigated the potential benefits of using supramolecular gel networks as reaction media to carry out air-sensitive metal-free light-induced trifluoromethylation of six-membered (hetero)arenes under aerobic conditions. This reaction was performed at room temperature (RT) using sodium triflinate (CF3SO2Na, Langlois' reagent) as a source of radicals and diacetyl as electron donor. The effects of confinement in gel media, concentration of reactants, and type of light source on yield and product distribution were evaluated and compared to the results obtained in homogeneous solution. Four different low molecular weight (LMW) gelators were employed in this study. The results confirmed the blocking effect of the gel medium against reaction quenching by external oxygen, as well as a certain control on the kinetics and selectivity.

CATALYST-FREE AND REDOX-NEUTRAL INNATE TRIFLUOROMETHYLATION AND ALKYLATION OF (HETERO)AROMATICS ENABLED BY LIGHT

The present disclosure relates to reagents and method for performing trifluoromethylation, difluoromethylation or alkylation of aromatic or heteroaromatic rings in a redox-neutral manner without any catalyst which are enabled by light. In addition, there are methods for synthesizing the starting reagents used in the trifluoromethylation, difluoromethylation or alkylation reactions.

Simple Photo-Induced Trifluoromethylation of Aromatic Rings

The trifluoromethylation of various aromatic compounds with Umemoto reagent II (2,8-difluoro-5-(trifluoromethyl)-5 H -dibenzo[ b, d ]thiophen-5-ium triflate) proceeded in moderate to good yields under simple photo-irradiation conditions without any cataly

Catalyst-Free and Redox-Neutral Innate Trifluoromethylation and Alkylation of Aromatics Enabled by Light

The Minisci alkylation is useful to functionalize aromatics via alkyl radical addition. Current approaches to prepare alkyl radicals follow either oxidative or reductive pathways from various functional groups. Developing new strategy beyond these traditional methods remains elusive yet highly significant. In this article, we present a redox-neutral and catalyst-free protocol to engender alkyl radicals in the context of trifluoromethylation and general alkylation of arenes. This protocol, via the Norrish type I concept to produce alkyl radicals, accommodates various functional groups and delivers the product in good yields. This method identified a series of compounds as the trifluoromethylation and alkylation reagents assisted by light. It is expected that these compounds can find potential applications in other radical-involved reactions.

Strongly Reducing, Visible-Light Organic Photoredox Catalysts as Sustainable Alternatives to Precious Metals

Photoredox catalysis is a versatile approach for the construction of challenging covalent bonds under mild reaction conditions, commonly using photoredox catalysts (PCs) derived from precious metals. As such, there is need to develop organic analogues as sustainable replacements. Although several organic PCs have been introduced, there remains a lack of strongly reducing, visible-light organic PCs. Herein, we establish the critical photophysical and electrochemical characteristics of both a dihydrophenazine and a phenoxazine system that enables their success as strongly reducing, visible-light PCs for trifluoromethylation reactions and dual photoredox/nickel-catalyzed C?N and C?S cross-coupling reactions, both of which have been historically exclusive to precious metal PCs.

Simple and Clean Photoinduced Aromatic Trifluoromethylation Reaction

We describe a simple, metal-and oxidant-free photochemical strategy for the direct trifluoromethylation of unactivated arenes and heteroarenes under either ultraviolet or visible light irradiation. We demonstrated that photoexcited aliphatic ketones, such as acetone and diacetyl, can be used as promising low-cost radical initiators to generate CF3 radicals from sodium triflinate efficiently. The broad utility of this strategy and its benefit to medicinal chemistry are demonstrated by the direct trifluoromethylation of unprotected bidentate chelating ligand, xanthine alkaloids, nucleosides, and related antiviral drug molecules.

Reactivity of a 10-I-3 hypervalent iodine trifluoromethylation reagent with phenols

(Chemical Equation Presented) The reaction of the 10-I-3 hypervalent iodine electrophilic trifluoromethylation reagent 1-trifluoromethyl-1,2-benziodoxol-3- (1H)-one (2) with 2,4,6-trimethylphenol, after deprotonation with NaH and in the presence of 18-crown-6 in a polar, nonprotic solvent, affords 1,3,5-trimethyl-2-(trifluoromethoxy)benzene (4) only as a byproduct. Trifluoromethylation occurs preferentially at the ortho- and para-positions of the aromatic core, giving the corresponding trifluoromethylcyclohexadienones 5 and 6. In case the ortho-and/or para-positions are not substituted, the corresponding products of an aromatic, electrophilic substitution are obtained in moderate yield, for example, 2-trifluoromethyl-4-tert-butylphenol (10a) from 4-tert-butylphenol (10).

ALKYLATION OF SODIUM 2,6-DI-TERT-BUTYLPHENOLATE BY PERFLUOROPROPYL AND METHYL IODIDES

Sodium 2,6-di-tert butylphenolate undergoes a condensation reaction with C3F7I with the formation of 2,6-di-tert-butyl-α-pentafluoroethyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexa-dien-1-ylidene)p-cresol, while in the reaction with CF3I a ring alkylation takes place with the formation of trifluoromethyl derivatives.

Trifluoromethylation of carbonyl compounds

A process which comprises reacting under substantially anhydrous conditions a perfluoroalkyltrihydrocarbylsilane and a carbonyl compound in the presence of a catalyst such that the carbonyl compound is perfluoroalkylated.

Electrochemically Induced Nucleophilic Substitution of Perfluoroalkyl Halides. An Example of a Dissociative Electron-Transfer-Induced Chemical Reaction

Nucleophilic substitution of perfluoroalkyl halides can be induced electrochemically.The reaction mechanism is a slightly modified version of the classical SRN1 mechanism in which the reaction is triggered by dissociative electron transfer, not