Catalysis for fluorination and trifluoromethylation

Abstract

Preface Recent advances in catalysis have made the incorporation of fluorine into complex organic molecules easier than ever before, but selective, general, and practical fluorination reactions remain sought after. Fluorination of molecules often imparts desirable properties such as metabolic and thermal stability, and fluorinated molecules are therefore frequently used as pharmaceuticals or materials. Even with the latest advances in chemistry, carbon–fluorine bond formation in complex molecules is still a significant challenge. Within the last few years, new reactions to make organofluorides have emerged and exemplify how to overcome some of the intricate challenges associated with fluorination.

Direct observation of two-electron Ag(I)/Ag(III) redox cycles in coupling catalysis

“…and found that the corresponding L 1 -X coupling products were obtained quantitatively ( [37][38][39] . DFT calculations show that the reductive elimination of L 5 -Ag(III) is strongly exergonic (DG ¼ À 25.8 kcal Á mol À 1 ) and has a very low barrier (DG a ¼ 8.6 kcal Á mol À 1 ; for computed reaction profile see Supplementary Fig.…”

First aromatic ring acetamidation by anodic oxidation

“…Trifluoromethylated arenes are important motifs in many pharmaceuticals, agrochemicals and organic materials due to the strong electron-withdrawing nature and the large hydrophobic domain of a CF 3 -group [1,2].…”

Regioselective trifluoromethylation of N-heteroaromatic compounds using trifluoromethyldifluoroborane activator

“…O rganic compounds containing trifluoromethyl (CF 3 ) group(s) are versatile components of drugs, agrochemicals and organic materials. The CF 3 group is highly electron withdrawing, and its introduction can remarkably improve molecular properties, such as lipophilicity, metabolic stability and bioavailability 1 .…”

“…The CF 3 group is highly electron withdrawing, and its introduction can remarkably improve molecular properties, such as lipophilicity, metabolic stability and bioavailability 1 . Therefore, the development of an efficient trifluoromethylation process is currently a main topic in organic synthesis [2][3][4][5][6][7][8][9] . Most current processes for accessing CF 3 containing molecules are performed by carboxy or trichloromethyl group substitution using hazardous fluorinating reagents under harsh reaction conditions 6 .…”

“…Therefore, the development of an efficient trifluoromethylation process is currently a main topic in organic synthesis [2][3][4][5][6][7][8][9] . Most current processes for accessing CF 3 containing molecules are performed by carboxy or trichloromethyl group substitution using hazardous fluorinating reagents under harsh reaction conditions 6 . Cross-coupling reactions between organohalides [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] or boronic acids (or their esters) [25][26][27][28][29][30][31][32][33][34] and trifluoromethylating reagents are another common approach.…”