Iron/Copper-Cocatalyzed Ullmann N,O-Arylation Using FeCl₃, CuO, and rac-1,1′-Binaphthyl-2,2′-diol

Abstract

We have developed an efficient and inexpensive bimetallic catalyst FeCl₃, CuO, and rac-BINOL that could promote N,O-arylation of aliphatic, arylamines, and phenols. The cross-coupling reaction conditions have high tolerance of various functional groups. This versatile and efficient iron/copper-cocatalyst can widely be used in the synthesis of the compounds containing ­(aryl)C-N or (aryl)C-O(aryl) bond.

copper - iron - cross-coupling - N-arylation - O-arylation

References and Notes

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17

General Procedure A: Coupling of Aryl Halides with Amines A flask was charged with FeCl₃ (16 mg, 0.1 mmol), CuO (8 mg, 0.1 mmol), Cs₂CO₃ (651 mg, 2 mmol), BINOL (57 mg, 0.2 mmol), and any remaining solids (amine and/or aryl halide). The flask was evacuated and backfilled with nitrogen (this procedure was repeated five times). Aryl halide (1 mmol, if liquid), amine (1.2 mmol, if liquid), and DMF (2 mL) were added to the flask under nitrogen atmosphere. The mixture was allowed to stir under nitrogen atmosphere at the shown temperature for the indicated period of time in the text (see Tables  [¹] and  [²] ). After cooling to r.t., the mixture was diluted with CH₂Cl₂ (ca. 20 mL), the solution was filtered, and the filter cake was further washed with CH₂Cl₂ (ca. 5 mL). The filtrate was washed with 1 M NaOH (ca. 10 mL). The combined aqueous phase was extracted with CH₂Cl₂ (2 × 10 mL). Organic layers were combined and dried over anhyd Na₂SO₄. The solvent of the filtrate was removed with the aid of a rotary evaporator, and the residue was purified by column chromatography on SiO₂ using PE-EtOAc (60:1 to 10:1) as eluent to provide the desired product.
1-Phenyl-1H-indole (5l):^¹6a yellow oil, yield 88%. ^¹H NMR (300 MHz, CDCl₃): δ = 7.61 (d, 1 H, J = 7.56 Hz), 7.42-7.51 (m, 5 H), 7.25-7.30 (m, 2 H), 7.13 (dd, 2 H, J = 9.60, 1.74 Hz), 6.61 (t, 1 H, J = 3.45 Hz). ^¹³C NMR (75 MHz, CDCl₃): δ = 139.9, 135.9, 129.7, 129.4, 128.1, 126.5, 124.5, 122.5, 121.2, 120.5, 110.6, 103.7. MS (EI): m/z = 193.23 [M⁺].

18

General Procedure B: Coupling of Aryl Halides with Phenols A flask was charged with FeCl₃ (16 mg, 0.1 mmol), CuO (8 mg, 0.1 mmol), Cs₂CO₃ (651 mg, 2 mmol), 1,1′-binaphthyl-2,2′-diol (57 mg, 0.2 mmol), and any remaining solids (phenol and/or aryl halide). The flask was evacuated and backfilled with nitrogen (this procedure was repeated five times). Aryl halide (1 mmol, if liquid), phenol (1.2 mmol, if liquid), and DMF (2 mL) were added to the flask under nitrogen atmosphere. The flask mixture was allowed to stir under nitrogen atmosphere at the shown temperature for the indicated period of time in the text (see Table  [³] ). After cooling to r.t., the mixture was diluted with CH₂Cl₂ (ca. 20 mL), the solution was filtered, and the filter cake was further washed with CH₂Cl₂ (ca. 5 mL). The solvent of the filtrate was removed with the aid of a rotary evaporator, and the residue was purified by column chromatography on SiO₂ using PE or PE-EtOAc (60:1 to 100:1) as eluent to provide the desired product.
1-(4-Chlorophenoxy)-3-methylbenzene (7f):^6d colorless oil, yield 79%. ^¹H NMR (300 MHz, CDCl₃): δ = 7.25 (dd, 2 H, J = 6.87, 2.07 Hz), 7.18 (d, 1 H, J = 7.53 Hz), 6.91 (dd, 3 H, J = 6.84, 2.04 Hz), 6.78 (s, 2 H), 2.31 (s, 3 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 157.0, 156.2, 140.2, 129.8, 129.7, 128.2, 124.6, 120.1, 119.8, 116.1, 21.5. MS (EI): m/z = 218.22 [M⁺].