Tamed Arene and Heteroarene Trifluoromethylation

Abstract

Scheme 2. Trifluoromethylation of arenes with well-defined sources of CuCF 3 , described by the groups of Vicic, [10a] Grushin, [10b] and Hartwig, [10c, d] (top) and of Grushin [11] (bottom). Bpin = pinacolylboryl.Scheme 3. CÀH trifluoromethylation, described by the groups of Yu [12] (top) and Liu [13a] and Qing [13b] (bottom).Scheme 4. CÀH radical trifluoromethylation of (hetero)arenes according to Nagib and MacMillan [14] (top) and Baran et al. [15] (bottom).

A class of effective decarboxylative perfluoroalkylating reagents: [(phen)2Cu](O2CRF)

“…[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35] There is, however, few examples for the introduction of the longer-chain perfluoroalkyl moieties, such as the C 2 F 5 group, into organic molecules (Scheme 2). 36,37,38 For instance, Hartwig and coworkers successfully employed stable (phen)Cu(C 2 F 5 ), prepared from reaction of CuOt-Bu with C 2 F 5 SiMe 3 , for pentafluoroethylation of arylboronate esters and heteroaryl bromides.…”

“…1 H NMR, 19 F NMR and 13 C NMR spectra were recorded using Bruker AVIII 400 spectrometer. 1 H NMR (chloroform δ 7.26) and 13 C NMR (chloroform δ 77.0).…”

Recent progress in the trifluoromethylation of alkenes with Togni's reagents

“…2,3 Hence, introduction of the trifluoromethyl group into alkenes has already become one of the hottest topics in pharmaceutical and agrochemical research. [4][5][6][7][8][9] Several years ago, Togni and co-workers 10 reported a conceptually new family of formally electrophilic CF 3 transfer reagents based on a cyclic hypervalent iodine(III) core, the most successful ones being Togni's reagents 1 and 2 (Scheme 1). These reagents are employed in the trifluoromethylation of phosphorus-, carbon-and oxygen-centered nucleophiles such as phosphines, 11 α-nitro-and β-keto-esters, 12,13 phosphorothioates, 14 aromatics, 15 alcohols, 16 sulfonic acids, 17 hydrogen phosphates, 18 aldehydes, 19 phenols, 20 arylboronic acids, 21 and quinones 22 .…”

Regioselective trifluoromethylation of N-heteroaromatic compounds using trifluoromethyldifluoroborane activator

“…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 .…”