Versatile Suzuki-Miyaura Coupling Reaction Using Diphenylvinylphosphine Ligands

Abstract

The scope of the utility of diphenylvinylphosphine ligands has been extended to include the Suzuki-Miyaura coupling reaction. A catalyst composed of phosphines and palladium efficiently mediates the reactions of a variety of aryl halides with arylboronic acids to afford the corresponding biphenyls in good to excellent yields.

cross-coupling - palladium - ligands - biaryls - halides

References and Notes

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10

For the preparation of 1b and 1c, see ref. 9.
Representative Procedure for the Preparation of 1a: A solution of 2-bromo-1,1-diphenylpropene⁹ (25.0 g, 91.5 mmol) and magnesium turnings (2.35 g, 96.1 mmol) in THF (100 mL) was stirred at r.t. under a nitrogen atmosphere. After addition of a piece of iodine, the solution was refluxed for 2 h. Then chlorodiisopropylphosphine (16.8 g, 109.8 mmol) was added dropwise at the same temperature and the mixed solution was refluxed for 18 h. After cooling to r.t., H₂O was added to the solution and the organic phase was extracted with toluene. The extract was dried over anhyd MgSO₄ and concentrated under reduced pressure. The concentrate was purified by recrystallization from MeOH (100 mL) to give the title compound (18.8 g, 66%) as a white solid. ¹H NMR (300 MHz, CDCl₃): δ = 1.07 (dd, J = 2.0, 7.1 Hz, 6 H), 1.12 (dd, J = 5.7, 6.3 Hz, 6 H), 1.80-2.04 (m, 2 H), 1.86 (d, J = 2.1 Hz, 3 H), 7.08-7.33 (m, 10 H). ¹³C NMR (75 MHz, CDCl₃): δ = 17.2 (d, J = 4.6 Hz), 20.8 (d, J = 1.1 Hz), 21.0 (d, J = 8.0 Hz), 24.4 (d, J = 14.3 Hz), 126.4, 126.5, 127.5, 128.1, 128.6, 130.2 (d, J = 3.5 Hz), 133.4 (d, J = 21.8 Hz), 143.5 (d, J = 8.6 Hz), 143.9 (d, J = 10.3 Hz), 155.3 (d, J = 32.0 Hz). ³¹P NMR (121 MHz, CDCl₃): δ = 5.44. HRMS (ESI): m/z [M + H]⁺ calcd for C₂₁H₂₇P: 311.1929; found: 311.1916.

11

Ligands 1a-c are solids stable enough to moisture and oxidation by molecular oxygen that they could be to be handled under air.

12

Typical Procedure for the Coupling Reaction: Aryl halide (1.0 equiv) and arylboronic acid (1.2 equiv) were added to a solution of KF (2.0 equiv), Pd(OAc)₂ (1.0 mol%) and ligand (2.0 mol%) in toluene (0.5 M) at r.t. under a nitrogen atmosphere. The solution was stirred at 80 °C for 1-3 h. After cooling to r.t., the solution was diluted with toluene, washed with H₂O and brine, dried over anhyd MgSO₄ and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography to give the coupling products. 4-Methoxybiphenyl (Table 1, entry 1): ¹H NMR (200 MHz, CDCl₃): δ = 3.85 (s, 3 H), 7.04-6.93 (m, 2 H), 7.60-7.23 (m, 7 H). ¹³C NMR (50 MHz, CDCl₃): δ = 55.3, 114.2, 126.6, 126.7, 128.1, 128.7, 133.8, 140.8, 159.1.