Trifluoromethylation of 1‐Aryl‐3,3‐diisopropyltriazenes

Hafner, Andreas; Bräse, Stefan

doi:10.1002/adsc.201201040

Cited by 33 publications

(9 citation statements)

References 53 publications

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“…Treatment of 2a (85.4 mg, 0.20 mmol) with 2-iodo-1-trifluoromethylbenzene 5f (112.2 μL, 217.6 mg, 0.8 mmol) by the Typical Procedure gave 6f (140.3 mg, 79%): 1 H NMR δ 7.38–7.48 (m, 7H), 7.53–7.58 (m, 1H), 7.74 (d, J = 8.0 Hz, 1H); 13 C NMR δ 124.1 (q, 1 J = 272.0 Hz), 126.0 (q, 3 J = 5.4 Hz), 127.3, 127.6, 127.7, 128.9, 128.4 (q, 2 J = 28.5 Hz), 131.3, 132.0, 139.9, 141.5. GC-MS ( t R 5.2 min) m / z 222 (100, M + ).…”

Section: Methodsmentioning

confidence: 99%

Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

Wang

Liang

et al. 2016

J. Org. Chem.

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Transition-metal-free LiCl-promoted cross-coupling reactions of tetraphenyltin, trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylstannanes with aryl halides in DMF provided access to biaryls in good to high yields. Up to four phenyl groups were transferred from the organostannanes substrates. The aryls bearing electron-withdrawing groups in either halides or organotin substrates gave coupling products in higher yields. The methodology has been applied for the efficient synthesis of ipriflavones.

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Section: Methodsmentioning

confidence: 99%

Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

Wang

Liang

et al. 2016

J. Org. Chem.

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“…Moreover, the triazene group can be activated by TMSI to give iodo pyridone 9 . In turn, 9 could be converted to trifluoromethyl-bearing pyridone 10 by a Cu-mediated transformation . In addition, 3ba is also suitable for transformations involving other nucleophiles (see Supporting Information for more details).…”

Section: Resultsmentioning

confidence: 99%

Alkynyl Triazenes as Fluoroalkyne Surrogates: Regioselective Access to 4-Fluoro-2-pyridones by a Rh(III)-Catalyzed C–H Activation–Lossen Rearrangement–Wallach Reaction

et al. 2020

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Fluorinated pyridones are an important scaffold displaying relevant biological activities. Efficient assembly strategies of pyridones are transition metal-catalyzed C–H annulations with alkynes. The inaccessibility and extreme lability of fluoro alkynes render any direct utilization in catalysis futile. We report a highly regioselective synthesis of 4-fluoro-2-pyridones using 1-alkynyl triazenes as a convenient fluoroalkyne surrogates. The protocol comprises an alkenyl C–H annulation with 1-alkynyl triazenes followed by a treatment with HF·pyridine smoothly delivering a broad range of 4-fluoro-2-pyridones in a one-pot fashion in 90 min at 23–60 °C. Notably, a rare Lossen rearrangement occurs during the C–H functionalization part of the transformation, allowing selective access to the less-available 4-fluoro-2-pyridone framework. Furthermore, the triazenyl intermediate was elaborated into additional fluorine-containing substituents like fluorinated alkoxy and trifluoromethyl groups.

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“…Amii and co-workers demonstrated copper-mediated cross-coupling reactions of Me 3 SiCF 2 CO 2 Et with aryl iodides containing electron-withdrawing, and electron-rich substituents. 101c, 105 The resulting esters were hydrolyzed and metal fluoride (KF or CsF) assisted protodecarboxylation was performed at 170 °C to obtain several aryldifluoromethyl compounds containing electron-withdrawing groups. However, substrates with halo and phenyl moieties required higher temperatures (200 °C) for decarboxylation, whereas electron-rich substrates failed to decarboxylate even at 200 °C.…”

Section: Scheme 26 Nucleophilic Addition To In Situ Formed Iminium Ionsmentioning

confidence: 99%

Silicon-Based Reagents for Difluoromethylation and Difluoromethylenation Reactions

Krishnamoorthy

Prakash

2017

Synthesis

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There have been significant developments in the area of perfluoroalkyl group transfer using silicon reagents, specifically in nucleophilic trifluoromethylation. The mild and versatile activation conditions bestow significant synthetic prowess to the silicon reagents in the area of fluoroalkylations. Owing to the importance of difluoromethylene (CF2) containing compounds in pharmaceuticals, materials, and agrochemicals, several CF2 group transfer methods using related silicon reagents have been developed and studied in detail. This review summarizes the recent developments and trends in this area.1 Introduction2 Trimethyl(trifluoromethyl)silane (Me3SiCF3)3 (Difluoromethyl)trimethylsilane (Me3SiCF2H)3.1 Nucleophilic Addition3.2 Nucleophilic Substitution3.3 Nucleophilic Difluoromethylation of Electron-Deficient Heterocycles3.4 Metal-Mediated Cross Coupling3.5 Oxidative Coupling of Terminal Alkynes4 Post-functionalizable Difluoromethyl Transfer Reagents4.1 (Chlorodifluoromethyl)trimethylsilane (Me3SiCF2Cl)4.2 (Bromodifluoromethyl)trimethylsilane (Me3SiCF2Br)4.3 [Difluoro(iodo)methyl]trimethylsilane (Me3SiCF2I)4.4 [Difluoro(phenylthio)methyl]trimethylsilane (Me3SiCF2SPh)4.5 [Difluoro(phenylsulfonyl)methyl]trimethylsilane (Me3SiCF2SO2Ph)4.6 Diethyl [Difluoro(trimethylsilyl)methyl]phosphonate [Me3SiCF2P(O)(OEt)2]4.7 Ethyl Difluoro(trimethylsilyl)acetate (Me3SiCF2CO2Et)4.8 Difluoro(trimethylsilyl)acetamides (Me3SiCF2CONR2)4.9 Difluoro(trimethylsilyl)acetonitrile (Me3SiCF2CN)5 Others6 Conclusions

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Trifluoromethylation of 1‐Aryl‐3,3‐diisopropyltriazenes

Cited by 33 publications

References 53 publications

Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

Transition-Metal-Free Cross-Coupling of Aryl Halides with Arylstannanes

Alkynyl Triazenes as Fluoroalkyne Surrogates: Regioselective Access to 4-Fluoro-2-pyridones by a Rh(III)-Catalyzed C–H Activation–Lossen Rearrangement–Wallach Reaction

Silicon-Based Reagents for Difluoromethylation and Difluoromethylenation Reactions

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