Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible‐Light Photoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(8), P. 2743 - 2747

Published: Jan. 21, 2016

The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range readily available mono-, di-, and trifluoromethyl heteroaryl can thus be used as efficient reagents under mild conditions. This method not only describes a new synthetic application sulfones, but also provides route to fluoroalkyl radicals.

Language: Английский

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Recent Progress toward the Introduction of Functionalized Difluoromethylated Building Blocks onto C(sp²) and C(sp) Centers

Chemistry - A European Journal, Journal Year: 2015, Volume and Issue: 21(37), P. 12836 - 12865

Published: July 14, 2015

Fluorine chemistry is a field undergoing tremendous expansion. Although much attention has been paid to the introduction of fluorine atom and CF3 group, less interest devoted functionalized fluorinated building blocks, in sharp contrast with high versatility products. In this Minireview, most relevant methods for difluoromethylated blocks are summarized. Access arenes, alkenes, alkynes highlighted special explanation reaction mechanism.

Language: Английский

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Fluorination methods in drug discovery

Organic & Biomolecular Chemistry, Journal Year: 2016, Volume and Issue: 14(36), P. 8398 - 8427

Published: Jan. 1, 2016

Late stage fluorination methods applied to biologically-active drugs have provided the pharmaceutical industry with new leads that show improved properties such as modulation of lipophilicity, electronegativity, basicity, bioavailability, and deceleration metabolic degradation.

Language: Английский

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Synthesis of Biaryls through Nickel‐Catalyzed Suzuki–Miyaura Coupling of Amides by Carbon–Nitrogen Bond Cleavage

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 55(24), P. 6959 - 6963

Published: April 21, 2016

The first Ni-catalyzed Suzuki-Miyaura coupling of amides for the synthesis widely occurring biaryl compounds through N-C amide bond activation is reported. reaction tolerates a wide range electron-withdrawing, electron-neutral, and electron-donating substituents on both partners. constitutes example generation aryl electrophiles from bench-stable with potential applications broad organometallic reactions.

Language: Английский

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Hypervalent iodine(iii) fluorinations of alkenes and diazo compounds: new opportunities in fluorination chemistry

Chemical Society Reviews, Journal Year: 2016, Volume and Issue: 45(22), P. 6270 - 6288

Published: Jan. 1, 2016

The review gives a timely overview on the fluoro functionalization of alkenes and diazo compounds using hypervalent λ³-iodane chemistry.

Language: Английский

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Catalytic Difluorination of Olefins

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(15), P. 5004 - 5007

Published: March 15, 2016

Molecular editing with fluorine is a validated strategy for modulating the structure and function of organic systems. In current arsenal catalytic dihalogenation technologies, direct generation vicinal difluoride moiety from simple olefins without prefunctionalization step remains conspicuously absent. Herein we report catalytic, difluorination displaying broad functional group tolerance, using inexpensive p-iodotoluene as catalyst. Preliminary efforts toward development an enantioselective variant are also disclosed.

Language: Английский

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Selective Single C(sp³)–F Bond Cleavage in Trifluoromethylarenes: Merging Visible-Light Catalysis with Lewis Acid Activation

Journal of the American Chemical Society, Journal Year: 2017, Volume and Issue: 139(51), P. 18444 - 18447

Published: Nov. 28, 2017

The conversion of easily available trifluoromethylarenes into aryldifluoromethyl compounds, which are valuable motifs in the pharmaceutical chemistry, is highly atom- and step-economical. However, single C(sp3)–F bond cleavage ArCF3 a great challenge because chemical inertness difficult selectivity control monodefluorination. We report here first example functionalization via visible-light catalysis merged with Lewis acid activation. method allows good chemoselectivity shows functional group tolerance. Mechanistic studies suggest an situ-generated borenium cationic species as key intermediate for this reaction.

Language: Английский

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Fluorine and Gold: A Fruitful Partnership

Chemical Reviews, Journal Year: 2016, Volume and Issue: 116(19), P. 11924 - 11966

Published: Aug. 22, 2016

Gold-catalyzed reactions have witnessed an exponential growth in the past decade. When unique modes of activation exhibited by gold species meet with either fluorinated building blocks or fluorinating reagents, new opportunities arise for development methodologies fluoroorganic chemistry. Indeed, and fluorine truly formed a very fruitful partnership, different types reactivity emerged from their combination. This review gives overview such endeavors. The special properties imparted to organic molecules been exploited gold-catalyzed processes, allowing generation unprecedented chemical entities. Thus, interaction salts has revised. In second section, recent developments nucleophilic fluorinations covered. catalysts that stabilize Au-F bond as well mechanistic studies field raised interest these C-F bonds. use electrophilic sources enabled catalysis. incorporation Selectfluor external oxidant constituted paradigm chemistry, incorporating elusive Au(I)/Au(III) redox couple transformations. strategy provided access both entities nonfluorinated derivatives means coupling reactions. Those topics reviewed last two sections.

Language: Английский

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Visible‐Light‐Induced Selective Defluoroborylation of Polyfluoroarenes, gem‐Difluoroalkenes, and Trifluoromethylalkenes

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(10), P. 4009 - 4016

Published: Dec. 18, 2019

Fluorinated organoboranes serve as versatile synthetic precursors for the preparation of value-added fluorinated organic compounds. Recent progress has been mainly focused on transition-metal catalyzed defluoroborylation. Herein, we report a photocatalytic defluoroborylation platform through direct B-H activation N-heterocyclic carbene boranes, synergistic merger photoredox catalyst and hydrogen atom transfer catalyst. This atom-economic operationally simple protocol enabled an extremely broad scope multifluorinated substrates including polyfluoroarenes, gem-difluoroalkenes, trifluoromethylalkenes in highly selective fashion. Intriguingly, can be free, regioselectivity obtained is complementary to reported transition-metal-catalysis many cases.

Language: Английский

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Ni/Cu-Catalyzed Defluoroborylation of Fluoroarenes for Diverse C–F Bond Functionalizations

Journal of the American Chemical Society, Journal Year: 2015, Volume and Issue: 137(45), P. 14313 - 14318

Published: Oct. 21, 2015

Ni/Cu-catalyzed transformation of fluoroarenes to arylboronic acid pinacol esters via C-F bond cleavage has been achieved. Further versatile derivatization an ester allowed for the facile two-step conversion a fluoroarene diverse functionalized arenes, demonstrating synthetic utility method.

Language: Английский

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