Silyldefluorination of Fluoroarenes by Concerted Nucleophilic Aromatic Substitution

Mallick, Shubhadip; Xu, Pan; Würthwein, Ernst‐Ulrich; Studer, Armido

doi:10.1002/ange.201808646

Cited by 21 publications

(13 citation statements)

References 60 publications

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“…A catalyst‐free strategy that does not require a transition metal to achieve the defluorosilylation is of great interest to chemists . Shortly afterwards, Studer and Würthwein reported the development of readily generated silyl lithium reagents with aryl fluorides to provide the corresponding aryl silanes . Meanwhile, Martin et al .…”

Section: Background and Originality Contentmentioning

confidence: 99%

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Gao

Wang

et al. 2019

Chin. J. Chem.

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of main observation and conclusion Silylated fluoroalkenes are important synthetic intermediates with complementary reactivity, which play a key role in the construction of natural products, pharmaceuticals, and manmade materials. Converting the normally highly stable fluoroalkenes into silylated fluoroalkenes by selective defluorosilylation is a challenging task. Herein, we report a simple, inexpensive and robust defluorosilylation of a variety of fluoroalkenes with silylboronates in the presence of alkoxy base to directly synthesize various silylated fluoroalkenes. The protocol features mild and safe reaction conditions that avoid a catalyst, a transition metal, a ligand, and high reaction temperature and tolerates a wide scope of fluoroalkene substrates without compromising the efficiency. Density functional theory calculations show that transient silyl anion complex undergoes an S N 2' or S N V substitution, which is responsible for this base-mediated defluorosilylation.1010 www.cjc.wiley-vch.de

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Section: Background and Originality Contentmentioning

confidence: 99%

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Gao

Wang

et al. 2019

Chin. J. Chem.

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“…S N Ar typically occurs under the temperature range of 0–100 °C depending on the energy required to activate the aryl moiety. 19 , 20 …”

Section: Introductionmentioning

confidence: 99%

“…S N Ar typically occurs under the temperature range of 0−100 °C depending on the energy required to activate the aryl moiety. 19,20 Fluorination has been applied onto a variety of organic compounds to provide liquid crystals with improved physical properties. 21,22 Nonetheless, the utilizations of S N Ar for the synthesis of fluorine-substituted aromatics have been mostly overlooked as an efficient strategy for the synthesis of fluorinesubstituted mesogenic compounds.…”

Section: Introductionmentioning

confidence: 99%

“…These consequent synthetic tactics were meant to reduce side reactions and cost and increase the purity of the produced liquid crystals. The produced polyethers and related intermediates were studied by 1 H/ 13 C/ 19 F NMR and infrared spectra. Different aliphatic diols were also employed to identify the length of the aliphatic chain for better liquid crystalline properties.…”

Section: Introductionmentioning

confidence: 99%

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Development of a Fluorescent Nanofibrous Template by In Situ S_NAr Polymerization of Fluorine-Containing Terphenyls with Aliphatic Diols: Self-Assembly and Optical and Liquid Crystal Properties

et al. 2021

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Stimulus-responsive supramolecular organogels have been broadly studied, but the assembly of a liquid crystalline organogel with a thermoreversible response remains a challenge. This could be attributed to the difficulty of designing organogelators with liquid crystalline properties. Nucleophilic aromatic substitution (S N Ar) has been utilized to produce a diversity of pentafluorobenzene-containing aromatics, which are very regioselective to para positions. Those pentafluorobenzene-functionalized aromatics have been ideal compounds for the preparation of calamitic liquid crystals. In this context, novel fluoroterphenyl-containing main-chain polyether (FTP@PE) was synthesized using in situ S N Ar polymerization as a convenient and effective synthetic strategy toward the development of fluorescent liquid crystals bearing fluoroterphenyl and ether groups. The fluoroterphenyl unit was synthesized by Cu(I)-supported decarboxylation cross-coupling of potassium pentafluorobenzoate and 1,4-diiodobenzene. The chemical structures of FTP@PE were studied with 1 H/ 13 C/ 19 F nuclear magnetic resonance and infrared spectra. The liquid crystal mesophases were determined with differential scanning calorimetry and polarizing optical microscopy. Ultraviolet–visible absorbance and emission spectral profiles showed solvatochromic activity. The nanofibrous morphologies were studied with a scanning electron microscope. The organogels of FTP@PE were developed in a number of solvents via van der Waals attraction forces of aliphatic moieties and π stacking of fluoroterphenyl groups. They demonstrated thermoreversible responsiveness.

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“…This finding not only revolutionized the understanding of the mechanistic aspects of these classical reactions but also suggested that, using SNAr chemistry, electron-rich arenes might be converted into a much wider range of products than previously anticipated. [7][8][9][10][11][12][13][14][15] Fluorinated arenes, on the other hand, have recently gained prominence in the areas of materials science and pharmaceutical chemistry owing to their distinct chemical and physiological properties, e.g., enhanced metabolic stability and improved lipophilicity. [16][17][18][19][20][21][22] However, there is no known natural source for fluoroarenes which means that these compounds must be prepared synthetically.…”

Section: Introductionmentioning

confidence: 99%

Studies on the Synthesis of Perfluoroaryl Sulfides and their Application in Desulfurative Nickel-Catalyzed Reductive Cross-Coupling

Lee

Hsu

Kao

et al. 2021

Preprint

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The C−S activation and sulfur removal from native thiols is challenging and limits the application of thiols as typical feedstock materials in organic synthesis despite their natural abundance. Herein, we describe a simple procedure to introduce a per-/polyfluoroaryl moiety, which serves as a redox-active scaffold, into alkyl/aryl thiols using nucleophilic aromatic substitution (SNAr) chemistry to activate the C−S bond. The per-/polyfluoroaryl group acts as an electron acceptor in single electron transfer events to generate radical intermediates through cleavage of the C−S bond of mercaptans and utilize them in nickel-catalyzed reductive cross-coupling reactions. In addition, using computational methods, we shed light on the mechanism of this class of SNAr reaction and show that the preference for a concerted or stepwise mechanistic pathway can be easily rationalized through a Marcus-type argument, as well as consideration of the relative stability of the potential energy surfaces.

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Silyldefluorination of Fluoroarenes by Concerted Nucleophilic Aromatic Substitution

Cited by 21 publications

References 60 publications

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Development of a Fluorescent Nanofibrous Template by In Situ S_NAr Polymerization of Fluorine-Containing Terphenyls with Aliphatic Diols: Self-Assembly and Optical and Liquid Crystal Properties

Studies on the Synthesis of Perfluoroaryl Sulfides and their Application in Desulfurative Nickel-Catalyzed Reductive Cross-Coupling

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Silyldefluorination of Fluoroarenes by Concerted Nucleophilic Aromatic Substitution

Cited by 21 publications

References 60 publications

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Transition‐Metal‐Free Defluorosilylation of Fluoroalkenes with Silylboronates

Development of a Fluorescent Nanofibrous Template by In Situ SNAr Polymerization of Fluorine-Containing Terphenyls with Aliphatic Diols: Self-Assembly and Optical and Liquid Crystal Properties

Studies on the Synthesis of Perfluoroaryl Sulfides and their Application in Desulfurative Nickel-Catalyzed Reductive Cross-Coupling

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Development of a Fluorescent Nanofibrous Template by In Situ S_NAr Polymerization of Fluorine-Containing Terphenyls with Aliphatic Diols: Self-Assembly and Optical and Liquid Crystal Properties