Cu-catalyzed trifluoromethylation of aryl iodides with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide

Abstract

SummaryThe trifluoromethylation of aryl iodides catalyzed by copper(I) salt with trifluoromethylzinc reagent prepared in situ from trifluoromethyl iodide and Zn dust was accomplished. The catalytic reactions proceeded under mild reaction conditions, providing the corresponding aromatic trifluoromethylated products in moderate to high yields. The advantage of this method is that additives such as metal fluoride (MF), which are indispensable to activate silyl groups for transmetallation in the corresponding reactions catalyzed by copper salt by using the Ruppert–Prakash reagents (CF3SiR3), are not required.

Catalytic trifluoromethylation of iodoarenes by use of 2-trifluoromethylated benzimidazoline as trifluoromethylating reagent

“…a Performed with 2a (0.050 mmol) and 1a (0.10 mmol) in solvent (1.0 mL). b Determined by 19 F NMR spectroscopy (benzotrifluoride was used as the internal standard).…”

“…The introduction of a trifluoromethyl group is one of the most attractive reactions in drug discovery [1,2]. In the past decade, trifluoromethylation reactions of aryl halides in the presence of transition-metal complexes were reported [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. CuCF 3 is a useful species for the trifluoromethylation of aryl halides and there are a number of precursors of CuCF 3 for trifluoromethylation reactions.…”

“…CuCF 3 is a useful species for the trifluoromethylation of aryl halides and there are a number of precursors of CuCF 3 for trifluoromethylation reactions. In contrast, the catalytic generation of CuCF 3 was less investigated [15][16][17][18][19][20][21]. For example, R 3 SiCF 3 , a fluoral derivative, and trifluoroacetates were employed as precursors of CuCF 3 species for the catalytic trifluoromethylation of iodoarenes ( Figure 1a) and the development of novel types of trifluoromethylating reagents is still desired.…”

The Synthesis and Evaluation of Fluoro‐, Trifluoromethyl‐, and Iodomuscimols as GABA Agonists

“…To explore this, we have carried out aD FT-based conformational Scheme3.Putative mechanism for the trifluoromethylationo f18. [17][18][19][20][21] Scheme4.Synthesis of iodomuscimol 5.a)33% HBrinAcOH,608C, 17 h, 19 %. bond approximately perpendicular to the aromatic ring, very similar to the X-ray structuref or 3 (see Computational Details in the Supporting Information).…”

Synthetic utility of dizinc reagents derived from 1,4-diiodo- and 1,4-dibromooctafluorobutane

“…Selected bond lengths (Å): C1-C5 1.5007(15); C1-C2 1.5376(17); C2-C3 1.5426(17); C3-C4 1.5426(17); C4-C13 1.5118(16). Selected bond angles (°): C5-C1-C2 116.29(9); C1-C2-C3 115.21(9); C2-C3-C4 116.63(10); C13-C4-C3 116.91(9); C14-C13-C4 124.53(10).Complex 4 is also capable of transmetalating [(dme)NiBr 2 ] to afford the known [(MeCN) 2 Ni(C 4 F 8 )] (13, eq 3), although 1b displays cleaner transmetalation reactivity. The acetonitrile ligands in 13 are labile, which makes 13 a useful synthetic precursor to a variety of [LNi(C 4 F 8 ] complexes.…”