Amido Pincer Nickel Catalyzed Kumada Cross-Coupling of Aryl, Heteroaryl, and Vinyl Chlorides

Abstract

Amido pincer nickel complexes {Ni(Cl)[2-P(Ph₂)C₆H₄NC(Ph)=NAr]} (Ar = 4-MeC₆H₄, 1; Ar = 4-ClC₆H₄, 2; Ar = 4-MeOC₆H₄, 3) were shown to efficiently catalyze the cross-coupling of activated, unactivated, and deactivated aryl chlorides, N-heteroaryl chlorides, 1,4-dichlorobenzene, and vinyl chlorides with aryl Grignard reagents.

Key words

nickel - cross-coupling - aryl Grignard reagent - aryl chloride - vinyl chloride

• References and Notes

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• 8 Representative Procedure for the Kumada Reaction A Schlenk tube was charged with 1 (2.8 mg, 0.005 mmol), THF (1.5 mL), and 2-chloroanisole (0.0718 g, 0.5 mmol). To the stirred solution was added dropwise a solution of 4-MeC₆H₄MgBr in THF (1.5 mL, 0.5 M in THF) at 30 °C. Stirring was continued at 30 °C for 24 h. The reaction was ceased by addition of H₂O (10 mL) and several drops of AcOH. The mixture was extracted with EtOAc (3 × 10 mL) and the combined organic layers were dried over anhyd Na₂SO₄. The Na₂SO₄ was removed by filtration and washed with EtOAc. The resulting solution was concentrated by rotary evaporation, and the residue was purified by column chromatography on silica gel (eluent: PE) to afford 1-methoxy-2-(p-tolyl)benzene (0.0917 g, 92%) as a white solid. ¹H NMR (300 MHz, CDCl₃): δ = 2.38 (s, 3 H, Me), 3.79 (s, 3 H, OMe), 6.95–7.08 (m, 2 H, C₆H₄), 7.21 (d, J = 7.8 Hz, 2 H, C₆H₄), 7.26–7.32 (m, 2 H, C₆H₄), 7.42 (d, J = 8.1 Hz, 2 H, C₆H₄). ¹³C NMR (75 MHz, CDCl₃): δ = 21.31, 55.66, 111.37, 120.94, 128.48, 128.86, 129.53, 130.92, 135.76, 136.69, 156.67.
• 9 ¹H NMR (300 MHz, CDCl₃): δ = 2.41 (s, 3 H, CH₃), 2.72 (s, 3 H, CH₃), 7.36 (d, J = 8.1 Hz, 2 H, C₆H₄), 7.50 (t, J = 7.2 Hz, 1 H, Ar), 7.67–7.71 (m, 2 H, Ar), 7.95 (d, J = 8.4 Hz, 1 H, Ar), 8.05 (d, J = 8.1 Hz, 2 H, C₆H₄), 8.15 (d, J = 8.4 Hz, 1 H, Ar). ¹³C NMR (75 MHz, CDCl₃): δ = 19.09, 21.44, 119.66, 123.68, 125.90, 127.26, 127.48, 129.33, 129.60, 130.29, 137.08, 139.31, 144.71, 148.23, 157.09.
• 10 ¹H NMR (300 MHz, CDCl₃): δ = 3.01 (s, 12 H, NCH₃), 6.84 (d, J = 7.5 Hz, 4 H, C₆H₄), 7.55 (d, 4 H, J = 8.7 Hz, C₆H₄), 7.60 (s, 4 H, C₆H₄). ¹³C NMR (75 MHz, CDCl₃): δ = 40.81, 113.07, 126.66, 127.18, 127.68, 139.04, 150.01.
• 11 ¹H NMR (300 MHz, CDCl₃): δ = 1.84 (s, 3 H, CH₃), 1.88 (s, 3 H, CH₃), 3.79 (s, 3 H, OCH₃), 6.21 (s, 1 H, CH), 6.85 (d, J = 8.7 Hz, 2 H, C₆H₄), 7.15 (d, J = 8.7 Hz, 2 H, C₆H₄). ¹³C NMR (75 MHz, CDCl₃): δ = 19.43, 26.94, 55.29, 113.55, 124.61, 129.90, 131.43, 134.05, 157.74.