scholarly journals AlBr3-Promoted stereoselective anti-hydroarylation of the acetylene bond in 3-arylpropynenitriles by electron-rich arenes: synthesis of 3,3-diarylpropenenitriles

2021 ◽  
Vol 17 ◽  
pp. 2663-2667
Author(s):  
Yelizaveta Gorbunova ◽  
Dmitry S Ryabukhin ◽  
Aleksander V Vasilyev
Keyword(s):  
Room Temperature ◽  
Triflic Acid ◽  
Aluminum Bromide

Reactions of 3-arylpropynenitriles (ArC≡CCN) with electron-rich arenes (Ar′H, benzene and its polymethylated derivatives) under the action of aluminum bromide (AlBr3, 6 equiv) at room temperature for 0.5–2 h result in the stereoselective formation of 3,3-diarylpropenenitriles (Ar(Ar′)C=CHCN) in yields of 20–64%, as products of mainly anti-hydroarylation of the acetylene bond. The obtained 3,3-diarylpropenenitriles in triflic acid CF3SO3H (TfOH) at room temperature for 1 h are cyclized into 3-arylindenones in yields of 55–70%.

scholarly journals Synthesis of 5-arylacetylene 1,2,4-oxadiazoles and their transformations under superelectrophilic activation conditions

2021 ◽  
Author(s):  
Andrey I Puzanov ◽  
Dmitry S Ryabukhin ◽  
Anna S Zalivatskaya ◽  
Dmitriy N Zakusilo ◽  
Darya S Mikson ◽  
...  
Keyword(s):  
Double Bond ◽  
Dft Calculations ◽  
Reaction Mechanisms ◽  
Room Temperature ◽  
Triflic Acid ◽  
Activation Conditions ◽  
First Time ◽  
Vinyl Triflates ◽  
Derivatives Of ◽  
Acetylene Derivatives

Acetylene derivatives of 1,2,4-oxadiazoles, 5-(2-arylethynyl)-3-aryl-1,2,4-oxadiazoles, have been obtained, for the first time, from 5-(2-arylethenyl)-3-aryl-1,2,4-oxadiazoles by their bromination at the carbon-carbon double bond followed by di-dehydrobromination with NaNH2 in liquid NH3.  Reaction of the acetylene 1,2,4-oxadiazoles with arenes in neat triflic acid TfOH (CF3SO3H) at room temperature for 1 h result in the formation of E-/Z-5-(2,2-diarylethenyl)-3-aryl-1,2,4-oxadiazoles as products of regioselective hydroarylation of the acetylene bond. Addition of TfOH to acetylene bond of these oxadiazoles gives rise quantitatively to E-/Z-vinyl triflates. Reaction cationic intermediates have been studied by DFT calculations. The reaction mechanisms have been discussed.

scholarly journals One-Pot Synthesis of (Z)-β-Halovinyl Ketones via the Cascade of Sonogashira Coupling and Hydrohalogenation

2021 ◽  
Vol 8 ◽  
Author(s):  
Fa-Jie Chen ◽  
Zhenguo Hua ◽  
Jianhui Chen ◽  
Jiajia Chen ◽  
Daesung Lee ◽  
...  
Keyword(s):  
Efficient Method ◽  
Room Temperature ◽  
Copper Catalyst ◽  
High Yield ◽  
Sonogashira Coupling ◽  
Terminal Alkynes ◽  
Acid Chlorides ◽  
Triflic Acid ◽  
One Pot

Herein, we report an efficient method for the synthesis of (Z)-β-halovinyl ketones through a one-pot Sonogashira coupling and hydrohalogenation reaction promoted by palladium-copper catalyst and Brønsted acid. The ynone intermediates are generated in situ from readily available acid chlorides and terminal alkynes at room temperature, which are directly converted to (Z)-β-halovinyl ketones by treating with triflic acid. This method avoids the use of an external halogen source and features broad substrate scope, high yield, and good to excellent stereoselectivity.

scholarly journals Superelectrophilic activation of 5-hydroxymethylfurfural and 2,5-diformylfuran: organic synthesis based on biomass-derived products

2016 ◽  
Vol 12 ◽  
pp. 2125-2135 ◽  
Author(s):  
Dmitry S Ryabukhin ◽  
Dmitry N Zakusilo ◽  
Mikhail O Kompanets ◽  
Anton A.Tarakanov ◽  
Irina A Boyarskaya ◽  
...  
Keyword(s):  
High Pressure ◽  
Nmr Spectroscopy ◽  
Dft Calculations ◽  
Organic Synthesis ◽  
Room Temperature ◽  
Trifluoromethanesulfonic Acid ◽  
Reaction Products ◽  
Triflic Acid ◽  
Pressure Tubes ◽  
Acidic Zeolites

The reaction of 5-hydroxymethylfurfural (5-HMF) with arenes in superacidic trifluoromethanesulfonic acid (triflic acid, TfOH) as the solvent at room temperature for 1–24 h gives rise to 5-arylmethylfurfurals (yields of 17–91%) and 2-arylmethyl-5-(diarylmethyl)furans (yields of 10–37%). The formation of these two types of reaction products depends on the nucleophilicity of the arene. The same reactions under the action of acidic zeolites H-USY in high pressure tubes at 130 °C for 1 h result in the formation of only 5-arylmethylfurfurals (yields of 45–79%). 2,5-Diformylfuran (2,5-DFF) in the reaction with arenes under the action of AlBr3 at room temperature for 1 h leads to 5-(diarylmethyl)furfurals (yields of 51–90%). The reactive protonated species of 5-HMF and 2,5-DFF were characterized by NMR spectroscopy in TfOH and studied by DFT calculations. These reactions show possibilities of organic synthesis based on biomass-derived 5-HMF and 2,5-DFF.

Probing the Reactivity of the Potent AgF2 Oxidizer. Part 1: Organic Compounds

2008 ◽  
Vol 73 (12) ◽  
pp. 1729-1746 ◽  
Author(s):  
Dorota Grzybowska ◽  
Przemysław Malinowski ◽  
Zoran Mazej ◽  
Wojciech Grochala
Keyword(s):  
Organic Compounds ◽  
Room Temperature ◽  
Bimolecular Reaction ◽  
Intramolecular Rearrangement ◽  
Triflic Acid ◽  
Experimental Conditions ◽  
Lewis Bases ◽  
Gaseous Products ◽  
Aliphatic Nitriles ◽  
High Degree

The reactivity of Ag(II)F2 towards a variety of organic compounds of a high degree of fluorination has been investigated. AgF2 readily fluorinates P(C6F5)3 to PF2(C6F5)3, and attacks the isothiocyanate functional group, -NCS, yielding Ag2S. Perfluorinated aliphatic nitriles resist the action of AgF2, but aromatic C6F5CN undergoes a radical-initiated oligomerization; byproducts include C6F6CN• and C6F5N2• (after intramolecular rearrangement following the bimolecular reaction). AgF2 oxidizes higher fluorosulfonic acids (C4F9SO3H, C8F17SO3H) at or close to the room temperature and triflic acid (CF3SO3H) at its boiling point to the corresponding peroxides. CF3COOH and CF3CONH2 are also decomposed in redox reactions, but the gaseous products have not been identified. Surprisingly, AgF2 is kinetically inert to perfluorinated aromatic hydrocarbons and to CCl4, but it decomposes CBr4 with vigorous elimination of Br2. CI4 decomposes explosively in the presence of AgF2. C6F5OH and CF3COOH are readily oxidized with AgF2 but, surprisingly, t-C4F9OH is kinetically resistant under similar conditions. Coordination complexes of perfluorinated aza and oxa Lewis bases (including perfluorinated 15-crown-5 ether) and AgF2 are not formed under the experimental conditions.

scholarly journals Umpolung of Indoles: Triflic Acid-Mediated C3-Regioselective Hy-droarylation of N-H Indoles

2022 ◽  
Author(s):  
Nazarii Sabat ◽  
Weiping Zhou ◽  
Vincent Gandon ◽  
Xavier Guinchard ◽  
Guillaume VINCENT
Keyword(s):  
Room Temperature ◽  
Atom Economy ◽  
Triflic Acid ◽  
Straightforward Manner ◽  
Biologically Relevant ◽  
Acetyl Group ◽  
High Yields

The direct dearomative addition of arenes to the C3-position of unprotected indoles is reported under operationally simple conditions with triflic acid at room temperature. The present regioselective hydroarylation is a straightforward manner to gen-erate an electrophilic indole at the C3-position without the need to introduce a deactivating acetyl group on the indolic nitrogen as in previously reported strategies. This atom economy method delivers biologically relevant 3-aryl indolines and 3,3-spiroindolines in high yields and regioselectivities from both intra and intermolecular processes.

The Action of Trifluoromethanesulfonic Acid on Naphthalene

1993 ◽  
Vol 46 (4) ◽  
pp. 427 ◽  
Author(s):  
A Launikonis ◽  
WHF Sasse ◽  
IR Willing
Keyword(s):  
Room Temperature ◽  
Complex Mixture ◽  
Trifluoromethanesulfonic Acid ◽  
Triflic Acid

Trifluoromethanesulfonic ( triflic ) acid reacts with naphthalene at room temperature to give a complex mixture from which five products have been isolated and identified as follows: (E)-3-benzylidene-2,3-dihydro-1H-benz[e]indene (2) (yield 15-20%), 1,2,3,4-tetrahydroanthracene (7) (c. 0.5%), 4-phenyl-1,2-dihydroanthracene (8), 3,4-dihydro-1,2′-binaphthyl (9a′), 4-(2-naphthyl)-1,2-dihydroanthracene (10) [yields of (8), (9a′) and (10) each less than 0.1%]. Also formed is (Z)-2-benzylidene-1,3-dihydro-1H-benz[e]indene (6) which is formed reversibly from (2) by the action of triflic acid. Mechanisms are proposed for the formation of these products.

scholarly journals Synthesis of 5-arylacetylenyl-1,2,4-oxadiazoles and their transformations under superelectrophilic activation conditions

2021 ◽  
Vol 17 ◽  
pp. 2417-2424
Author(s):  
Andrey I Puzanov ◽  
Dmitry S Ryabukhin ◽  
Anna S Zalivatskaya ◽  
Dmitriy N Zakusilo ◽  
Darya S Mikson ◽  
...  
Keyword(s):  
Double Bond ◽  
Dft Calculations ◽  
Reaction Mechanisms ◽  
Room Temperature ◽  
Triflic Acid ◽  
Activation Conditions ◽  
First Time ◽  
Vinyl Triflates ◽  
Derivatives Of ◽  
Acetylene Derivatives

Acetylene derivatives of 1,2,4-oxadiazoles, i.e., 5-(2-arylethynyl)-3-aryl-1,2,4-oxadiazoles, have been obtained, for the first time reported, from 5-(2-arylethenyl)-3-aryl-1,2,4-oxadiazoles by their bromination at the carbon–carbon double bond followed by di-dehydrobromination with NaNH2 in liquid NH3. The reaction of the acetylenyl-1,2,4-oxadiazoles with arenes in neat triflic acid TfOH (CF3SO3H) at room temperature for 1 h resulted in the formation of E/Z-5-(2,2-diarylethenyl)-3-aryl-1,2,4-oxadiazoles as products of regioselective hydroarylation of the acetylene bond. The addition of TfOH to the acetylene bond of these oxadiazoles quantitatively resulted in E/Z-vinyl triflates. The reactions of the cationic intermediates have been studied by DFT calculations and the reaction mechanisms are discussed.

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