Nucleophilic trifluoromethylation

Trifluoromethylation and pentafluorophenylation of enamines

“…8,10 effectivity of this reagent in comparison with tris(penta fluorophenyl)silyl derivatives. 4 Experimental 1 H, 13 C, and 19 F NMR spectra were recorded on a Bruker AM 300, Bruker WM 250, or Bruker AC 200 spectrometers in CDCl 3 . Dimethylformamide was distilled in vacuo over P 2 O 5 and kept over molecular sieves 4 Å. Enamines 1a-d 15 and 1e 16 and Me 3 SiC 6 F 5 17,18 were obtained according to the known pro cedures, Me 3 SiCF 3 was purchased from PiM Invest.…”

“…For compounds 4c,e, the formed product was dissolved in light petroleum, washed with water (3×10 mL), dried with Na 2 SO 4 , concentrated, and the residue was distilled in vacuo. 13 C NMR, δ: 8.5 (CH 3 ); 23.9 (CH 2 CH 2 ); 28.6 (CH 2 CH 3 ); 46.3 (CH 2 NCH 2 ); 68.9 (q, CCF 3 , J C,F = 22.1 Hz); 127.3 (CH Ph ); 127.5 (q, CH Ph , J C,F = 2.6 Hz); 127.9 (CH Ph ); 129.6 (q, CF 3 , J C,F = 298.9 Hz); 138.3 (ipso C Ph ). 19 13 C NMR, δ: 20.4 (CH 2 ); 24.4 (CH 2 ); 25.3 (CH 2 ); 28.4 (q, CH 2 , J C,F = 1.6 Hz); 44.4 (q, CH 2 NCH 2 , J C,F = 1.6 Hz); 59.7 (q, CCF 3 , J C,F = 21.5 Hz); 129.5 (q, CF 3 , J C,F = 298.9 Hz).…”

“…13 C NMR, δ: 8.5 (CH 3 ); 23.9 (CH 2 CH 2 ); 28.6 (CH 2 CH 3 ); 46.3 (CH 2 NCH 2 ); 68.9 (q, CCF 3 , J C,F = 22.1 Hz); 127.3 (CH Ph ); 127.5 (q, CH Ph , J C,F = 2.6 Hz); 127.9 (CH Ph ); 129.6 (q, CF 3 , J C,F = 298.9 Hz); 138.3 (ipso C Ph ). 19 13 C NMR, δ: 20.4 (CH 2 ); 24.4 (CH 2 ); 25.3 (CH 2 ); 28.4 (q, CH 2 , J C,F = 1.6 Hz); 44.4 (q, CH 2 NCH 2 , J C,F = 1.6 Hz); 59.7 (q, CCF 3 , J C,F = 21.5 Hz); 129.5 (q, CF 3 , J C,F = 298.9 Hz). 19 13 C NMR, δ: 24.0 (CH 2 ); 24.7 (CH 2 ); 31.7 (CH 2 ); 46.6 (q, CH 2 NCH 2 , J C,F = 1.4 Hz); 69.6 (q,…”

Selective fluorination of substituted trichloromethyl benzenes by HF in liquid phase: Preparation of fluorinated building blocks

“…These changes make them suitable for diverse applications in the areas of material science, agrochemistry and pharmaceuticals [4][5][6]. While a wide variety of methods have been developed for introducing trifluoromethyl groups into organic molecules [7][8][9][10][11], the fluorine-chlorine exchange is the most widely used technology in industrial scale especially for the selective synthesis of fluorinated building blocks. This reaction can be carried out using two different sources of fluorine: alkali metal fluorides, such as potassium fluoride (KF) [12], or anhydrous hydrogen fluoride (HF).…”

Catalytic Enantioselective Trifluoromethylation of Azomethine Imines with Trimethyl(trifluoromethyl)silane

“…Although the first report on the nucleophilic trifluoromethylation of carbonyl compounds using tetrabutylammonium fluoride by Prakash and Olah [1,2] was reported over 20 years ago, the enantioselective nucleophilic trifluoromethylation using trimethyl(trifluoromethyl)silane, Me 3 SiCF 3 , remains a challenge in fluoroorganic chemistry. Although a variety of methodologies for catalytic asymmetric reactions are now available in modern organic synthesis, chiral auxiliary based diastereoselective trifluoromethylation [3] is still the most widely applied approach in the field of fluorine chemistry with enantioselective catalysis remaining a big challenge.…”