Difluoro(trimethylsilyl)acetonitrile: Synthesis and Fluoroalkylation Reactions

Kosobokov, Mikhail D.; Dilman, Alexander D.; Levin, Vitalij V.; Стручкова, Марина И.

doi:10.1021/jo301094b

Cited by 68 publications

(38 citation statements)

References 22 publications

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“…In recent years, Prakash and co-workers have discovered two Freon-free methods for the synthesis of TMSCF 3 from fluoroform (CF 3 H), which paved the way for the synthetic applications of TMSCF 3 [38–39]. Moreover, the preparation of TMSCF 2 Br either by fluoro–bromo exchange reaction of TMSCF 3 [34] or by bromination of TMSCF 2 H [34,40] has also been disclosed. To obtain TMSCF 2 Cl, we tried the halogen exchange reaction of TMSCF 2 Br.…”

Section: Resultsmentioning

confidence: 99%

Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine

Wang¹,

Li²,

Ni³

et al. 2014

Beilstein J. Org. Chem.

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Summary Background: 1,1-Difluoroalkenes cannot only be used as valuable precursors for organic synthesis, but also act as bioisosteres for enzyme inhibitors. Among various methods for their preparation, the carbonyl olefination with difluoromethylene phosphonium ylide represents one of the most straightforward methods. Results: The combination of (chlorodifluoromethyl)trimethylsilane (TMSCF2Cl) and triphenylphosphine (PPh3) can be used for the synthesis of gem-difluoroolefins from carbonyl compounds. Comparative experiments demonstrate that TMSCF2Cl is superior to (bromodifluoromethyl)trimethylsilane (TMSCF2Br) and (trifluoromethyl)trimethylsilane (TMSCF3) in this reaction. Conclusion: Similar to many other Wittig-type gem-difluoroolefination reactions in the presence of PPh3, the reaction of TMSCF2Cl with aldehydes and activated ketones is effective.

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Section: Resultsmentioning

confidence: 99%

Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine

Wang¹,

Li²,

Ni³

et al. 2014

Beilstein J. Org. Chem.

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“…(Trifluoromethyl)trimethylsilane was purchased from Oakwood Chemical (Estill, SC, USA). (Difluoromethyl)trimethylsilane [23], (bromodifluoromethyl)trimethylsilane [24], (chlorodifluoromethyl)trimethylsilane [25], (tribromomethyl)trimethylsilane [26] and (trichloromethyl)trimethylsilane [27] were prepared according to reported procedures. 1 H, 11 B and 19 F NMR spectra were recorded on Bruker Avance-III 300 MHz instrument in CDCl 3 or CDC 3 N. Chemical shifts are reported in ppm.…”

Section: Methodsmentioning

confidence: 99%

Insertion of Carbenes into Deprotonated nido-Undecaborane, B11H13(2-)

2019

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We have examined the insertion of carbenes carrying leaving groups into the [nido-B11H13]2− dianion to form the [closo-1-CB11H12]− anion. The best procedure uses CF3SiMe3 and LiCl as the source of CF2. It is simple, convenient and scalable and proceeds with 70–90% yield. Density functional calculations have been used to develop a mechanistic proposal that accounts for the different behavior of CF2, requiring only one equivalent of base for successful conversion of Na[nido-B11H14]− to [closo-1-CB11H12]−, and CCl2 and CBr2, which require more.

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“…29b, 49 For example, direct treatment of Me 3 SiCF 3 (1) with BBr 3 gave (bromodifluoromethyl)trimethylsilane (Me 3 SiCF 2 Br, 4) in 52% yield, whereas Me 3 SiCF 2 H (2) was brominated using radical bromine sources such as NBS to obtain Me 3 SiCF 2 Br (4) in 75-80% yield. 53,54 Scheme 14 First example of direct nucleophilic bromodifluoromethylation Though Me 3 SiCF 2 Br (4) was reported in 1990, 55 unlike the Ruppert-Prakash reagent and Me 3 SiCF 2 Cl, the direct nucleophilic transfer of CF 2 Br using initiators such as fluoride from the corresponding silicon reagent to electrophiles such as aldehydes was reported to be unsuccessful, except for one select example (Scheme 14). 30 Such a behavior is attributed to the ability of the BrCF 2 anion to readily α-eliminate bromide to form the singlet difluoromethylene under the reaction conditions.…”

Section: (Bromodifluoromethyl)trimethylsilane (Me 3 Sicf 2 Br)mentioning

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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Difluoro(trimethylsilyl)acetonitrile: Synthesis and Fluoroalkylation Reactions

Abstract: A new silicon reagent, difluoro(trimethylsilyl)acetonitrile, was prepared by insertion of difluorocarbene into silyl cyanide. The obtained silane served as a good cyanodifluoromethylating reagent toward aldehydes, N-tosylimines, N-alkylimines, and enamines under basic or acidic conditions.

Cited by 68 publications

References 22 publications

Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine

Deoxygenative gem-difluoroolefination of carbonyl compounds with (chlorodifluoromethyl)trimethylsilane and triphenylphosphine

Insertion of Carbenes into Deprotonated nido-Undecaborane, B11H13(2-)

Silicon-Based Reagents for Difluoromethylation and Difluoromethylenation Reactions

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