Difluoromethylation Reactions of Organic Compounds

Chemistry - A European Journal, Journal Year: 2017, Volume and Issue: 23(59), P. 14676 - 14701

Published: June 20, 2017

Abstract The relevance of the ‐CF 2 H moiety has attracted considerable attention from organic synthetic and medicinal chemistry communities, because this group can act as a more lipophilic isostere carbinol, thiol, hydroxamic acid, or amide groups. Being weakly acidic, CF establish hydrogen‐bonding interactions to improve binding selectivity biologically active compounds. Therefore, hydroxyl, amino, thio substituents lead structures are routinely replaced by motif in drug discovery, with great benefits pharmacological activity drugs candidates agrochemicals. Consequently, late‐stage introduction is sought‐after strategy designing bioactive Secondly, but nonetheless relevant meaningful, study pathways introduce −Y (Y≠H, F) into substrates compounds that contain functionality have also found vast applications other areas, such fungicides, insecticides, etc., thus, deserves special attention. Although emphasis made on difluoromethylation strategies functionalize different families compounds, three main methodological protocols will be presented review article for Y moieties substrates: i) metal‐photoredox catalysis; ii) through transition metal‐catalyzed thermal protocols; iii) transition‐metal‐free strategies.

Language: Английский

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The Fluorination of C−H Bonds: Developments and Perspectives

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(42), P. 14824 - 14848

Published: Feb. 13, 2019

Abstract This Review summarizes advances in fluorination by C(sp 2 )−H and 3 activation. Transition‐metal‐catalyzed approaches championed palladium have allowed the installation of a fluorine substituent at ) sites, exploiting reactivity high‐oxidation‐state transition‐metal fluoride complexes combined with use directing groups (some transient) to control site stereoselectivity. The large majority known methods employ electrophilic reagents, but combining nucleophilic source an oxidant appeared. External ligands proven be effective for directed weakly coordinating auxiliaries, thereby enabling over reactivity. Methods relying on formation radical intermediates are complementary transition‐metal‐catalyzed processes as they allow undirected fluorination. To date, C−H fluorinations mainly N−F reagents unique Mn III ‐catalyzed oxidative using has been developed. Overall, field late‐stage progressed much more slowly, state play explaining why 18 F‐fluorination is still its infancy.

Language: Английский

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New Horizons of Photocatalytic Fluoromethylative Difunctionalization of Alkenes

Chem, Journal Year: 2017, Volume and Issue: 4(3), P. 409 - 437

Published: Dec. 21, 2017

Language: Английский

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Electrochemical Difluoromethylarylation of Alkynes

Journal of the American Chemical Society, Journal Year: 2018, Volume and Issue: 140(7), P. 2460 - 2464

Published: Feb. 6, 2018

An unprecedented radical difluoromethylarylation reaction of alkynes has been developed by discovering a new difluoromethylation reagent, CF2HSO2NHNHBoc. This air-stable and solid reagent can be prepared in one step from commercially available reagents CF2HSO2Cl NH2NHBoc. The CF2H radical, generated through ferrocene-mediated electrochemical oxidation, participates an unexplored alkyne addition followed challenging 7-membered ring-forming homolytic aromatic substitution to afford fluorinated dibenzazepines.

Language: Английский

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Contemporary synthetic strategies in organofluorine chemistry

Nature Reviews Methods Primers, Journal Year: 2021, Volume and Issue: 1(1)

Published: July 8, 2021

Language: Английский

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Fluoroalkylation reactions in aqueous media: a review

Green Chemistry, Journal Year: 2018, Volume and Issue: 20(8), P. 1662 - 1731

Published: Jan. 1, 2018

Recent advances in aqueous fluoroalkylation using various reagents are summarized this review.

Language: Английский

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Iron-Catalyzed Difluoromethylation of Arylzincs with Difluoromethyl 2-Pyridyl Sulfone

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 140(3), P. 880 - 883

Published: Dec. 26, 2017

We report the first iron-catalyzed difluoromethylation of arylzincs with difluoromethyl 2-pyridyl sulfone via selective C–S bond cleavage. This method employs readily available, bench-stable fluoroalkyl reagent and inexpensive iron catalyst, allowing facile access to structurally diverse difluoromethylated arenes at low temperatures. The experiment employing a radical clock indicates involvement species in this process.

Language: Английский

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Progress in Difluoroalkylation of Organic Substrates by Visible Light Photoredox Catalysis

Advanced Synthesis & Catalysis, Journal Year: 2019, Volume and Issue: 361(7), P. 1500 - 1537

Published: Jan. 17, 2019

Abstract The selective incorporation of fluorinated motifs, in particular CF 2 FG (FG=a functional group) and H groups, into organic compounds has attrracted increasing attention since organofluorine molecules are the utmost importance areas nuclear imaging, pharmaceutical, agrochemical, material sciences. A variety synthetic approaches been employed late‐stage difluoroalkylation reactions. Visible light photoredox catalysis for production radicals provided a more sustainable alternative to other conventional radical‐triggered reactions from viewpoint safety, cost, availability, “green” chemistry. wide range difluoroalkylating reagents successfully implemented these transformations presence transition metal complexes or photocatalysts. In most cases, upon excitation via visible irradiation with fluorescent bulbs blue light‐emitting diode (LED) lamps, photocatalysts can act as both reductive oxidative quenchers, thus enabling application electron‐donor electron‐acceptor generation radicals. Subsequent radical addition substrates additional afford corresponding difluoroalkylated derivatives. present review describes distinct strategies metal‐ organic‐photocatalyzed broad by reported literature 2014. magnified image

Language: Английский

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Metallaphotoredox Difluoromethylation of Aryl Bromides

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(38), P. 12543 - 12548

Published: Aug. 3, 2018

Herein, we report a convenient and broadly applicable strategy for the difluoromethylation of aryl bromides by metallaphotoredox catalysis. Bromodifluoromethane, simple commercially available alkyl halide, is harnessed as an effective source difluoromethyl radical silyl-radical-mediated halogen abstraction. The merger this fluoroalkyl electrophile activation pathway with dual nickel/photoredox catalytic platform enables diverse array heteroaryl under mild conditions. utility procedure showcased in late-stage functionalization several drug analogues.

Language: Английский

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Organofluorine chemistry: promising growth areas and challenges

Russian Chemical Reviews, Journal Year: 2019, Volume and Issue: 88(5), P. 425 - 569

Published: March 29, 2019

Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area organic chemistry. Fluorine present in molecule largely determines its specific chemical biological properties. This thematic issue covers trends that have been actively developed Russia last 15 – 20 years. The review describes nucleophilic substitution heterocyclization reactions involving fluorinated arenes quinones skeletal cationoid rearrangements polyfluoroarene series. transformations CF 3 -substituted carbocations radical cations are considered. Heterocyclization oxidative addition trifluoroacetamide derivatives moiety polyfluorinated organoboranes borates with retention carbon boron bond discussed. Particular attention devoted to catalytic olefination using freons as an efficient synthetic route compounds. application unsymmetrical fluorine-containing N-heterocyclic carbene ligands catalysts for olefin metathesis demonstrated. A variety classes considered, particular, 1,2-diaminobenzenes, 1-halo-2-trifluoroacetylacetylenes, α -fluoronitro compounds, heterocycles, 2-hydrazinylidene-1,3-dicarbonyl derivatives, imines silanes. potential practical applications fundamental chemistry, materials science biomedicine outlined. bibliography includes 1019 references.

Language: Английский

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