Practical and Convenient Suzuki-Miyaura
Coupling Reaction and α-Arylation Using Diphenylcyclopropylphosphine
Ligands

Ken Suzuki; Tomoya Sawaki; Yoji Hori; Tohru Kobayashi

doi:10.1055/s-2008-1078525

LETTER

Practical and Convenient Suzuki-Miyaura Coupling Reaction and α-Arylation Using Diphenylcyclopropylphosphine Ligands

Ken Suzuki*, Tomoya Sawaki, Yoji Hori, Tohru Kobayashi
Takasago International Corporation, Corporate Research & Development Division, 1-4-11 Nishi-yawata, Hiratsuka, Kanagawa 254-0073, Japan
Fax: +81(463)252093; e-Mail: ken_suzuki@takasago.com;

Abstract

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Abstract

A new ligand, diphenylmethylcyclopropylphosphine, has successfully been applied in the palladium-catalyzed Suzuki-Miyaura coupling and α-arylation of ketones with aryl chlorides in moderate to high yields. An asymmetric coupling between anisyl chloride and 2-methylindan-1-one was also tested as the first trial, giving 80% yield and 41% ee with 1 mol% of Pd.

Key words

cross-coupling - halides - ligands - palladium

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References and Notes

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For optically pure phosphine 1, it is now under investigation.

Phosphine ligand 2 was prepared with the same manner as ligand 1, see ref. 15a. ^¹H NMR (500 MHz, CDCl₃): δ = 0.99-1.40 (m, 11 H), 1.01 (d, J = 1.7 Hz, 3 H), 1.55-1.93 (m, 13 H), 7.00 (t, J = 7.6 Hz, 1 H), 7.07 (t, J = 7.6 Hz, 1 H), 7.12 (t, J = 7.6 Hz, 2 H), 7.19 (d, J = 7.6 Hz, 2 H), 7.28-7.37 (m, 4 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 20.4 (d, J = 4.4 Hz), 23.9 (d, J = 17.1 Hz), 26.52, 26.54, 27.0 (d, J = 12.6 Hz), 27.36, 27.44 (d, J = 3.9 Hz), 27.9 (d, J = 4.0 Hz), 28.3 (d, J = 15.5 Hz), 29.5, 30.1 (d, J = 8.9 Hz), 31.8 (d, J = 20.1 Hz), 32.7 (d, J = 15.5 Hz), 34.2 (d, J = 25.3 Hz), 34.6 (d, J = 15.8 Hz), 40.6 (d, J = 10.9 Hz), 125.9, 126.1, 127.9, 128.2, 129.8 (d, J = 2.5 Hz), 130.3 (d, J = 1.3 Hz), 143.8 (d, J = 8.8 Hz), 143.9. ^³¹P NMR (202 MHz, CDCl₃): δ = 11.21. ESI-HRMS: m/z calcd for C₂₈H₃₇P [M + Na]⁺: 427.2531; found [M + Na]⁺: 427.2534.

Optically pure phosphine 2 was prepared by oxidation of phosphine with H₂O₂, HPLC resolution and the following reduction by Cl₃SiH.
Oxidation of Phosphine Ligand 2
H₂O₂ (30% in H₂O, 1.26 g, 11.1 mmol) was added dropwise to a solution of phosphine 2 (3.00 g, 7.42 mmol) in toluene (15 mL) at 0 ˚C. After the mixture was stirred at 35 ˚C for 2 h, an organic phase was separated, washed with 20% aq Na₂SO₃ and H₂O, dried over anhyd MgSO₄, and concentrated under reduced pressure to give a crude oxide (3.14 g, quantitative yield) as a white solid. The crude was used for chiral resolution without further purification. ^¹H NMR (500 MHz, CDCl₃): δ = 1.09 (d, J = 11.8 Hz, 3 H), 1.15-1.32 (m, 7 H), 1.33-2.23 (m, 16 H), 2.52 (dd, J = 4.7, 12.9 Hz, 1 H), 7.07 (t, J = 7.3 Hz, 1 H), 7.14-7.21 (m, 3 H), 7.24-7.32 (m, 2 H), 7.39-7.50 (m, 4 H). ^¹³C NMR (125 MHz, CDCl₃): δ = 19.9, 20.0, 23.51, 23.53, 23.9, 24.5, 25.36, 25.40, 25.91, 25.95, 25.98, 26.11, 26.12, 26.25, 26.3, 26.6, 26.7, 27.28, 27.34, 27.37, 27.44, 27.53, 27.55, 28.37, 28.39, 35.4, 35.9, 38.8, 39.3, 40.46, 40.48, 126.1, 126.4, 127.6, 128.5, 129.6, 129.9, 141.64, 141.66, 143.4 (observed complexity due to P-C splitting). ^³¹P NMR (202 MHz, CDCl₃): δ = 49.88. ESI-HRMS: m/z calcd for C₂₈H₃₇PO [M + H]⁺: 241.2660; found [M + H]⁺: 241.2656.
HPLC Resolution of Racemic Oxide of Phosphine 2
The optically pure oxide was obtained by HPLC resolution with a Chiralcel OD-H column (250 mm × 20 mm, hexane-2-PrOH = 96:4, flow rate = 10 mL/min).
Reduction of Oxide of Phosphine 2
Under a nitrogen atmosphere, SiCl₃H (2.26 g, 16.7 mmol) was added dropwise to a solution of optically pure phosphine oxide (1.00 g, 2.38 mmol) and N,N-dimethylaniline (2.31 g, 19.0 mmol) in xylene (16 mL) at 85 ˚C. After stirring at 115 ˚C for 1.5 h, remaining SiCl₃H was removed from the reaction solution by distillation. The solution was washed with 20% aq NaOH and H₂O, dried over anhyd MgSO₄, and concentrated under reduced pressure. The concentrate was purified by recrystallization from toluene (1.5 mL) and MeOH (6 mL) to give the optically pure phosphine 2 as a white solid (0.49 g, 51%).

Typical Procedure for the Coupling Reaction of Aryl Halides with Arylboronic Acids
A solution of powdered K₂CO₃ (2.0 equiv), [(π-allyl)PdCl]₂ (0.5 mol%) and ligand (2.0 mol%) in toluene (0.5 M) was stirred for 15 min at r.t. Arylboronic acid (1.5 equiv) and aryl halide (1.0 equiv) were added to the premixed solution. The mixture was stirred at 80 ˚C for the time specified. After cooling to r.t., the reaction solution was diluted with toluene, washed with H₂O, dried over MgSO₄, and concentrated under reduced pressure. Purification of the concentrate by column chromatography on SiO₂ gave the coupling product.
4-Methoxy-4′-methylbiphenyl (Table 1, Entry 3)
Purification by flash chromatography (hexane-toluene = 2:1) gave a white solid. ^¹H NMR (300 MHz, CDCl₃): δ = 2.38 (s, 3 H), 3.84 (s, 3 H), 6.96 (d, J = 9.0 Hz, 2 H), 7.22 (d, J = 8.0 Hz, 2 H), 7.44 (d, J = 8.0 Hz, 2 H), 7.50 (d, J = 9.0 Hz). ^¹³C NMR (75 MHz, CDCl₃): δ = 21.0, 55.3, 114.1, 126.6, 127.9, 129.4, 133.7, 136.3, 138.0, 158.9.

Typical Procedure for the Coupling Reaction of Aryl Halides with Ketones
A solution of NaOt-Bu (1.2 equiv), [(π-allyl)PdCl]₂ (0.5 mol%) and ligand (2.0 mol%) in toluene (0.5 M) was stirred for 15 min at r.t. Aryl halide (1.0 equiv) and ketone (1.1 equiv) were added to the solution. The mixture was stirred at 80 ˚C for the time specified. After cooling to r.t., the reaction solution was diluted with toluene, washed with H₂O, dried over MgSO₄, and concentrated under reduced pressure. Purification of the concentrate by column chromatography on SiO₂ gave the coupling product.
2-(4-Methoxyphenyl)propiophenone (Table 1, Entry 7)
Purification by flash chromatography (hexane-EtOAc = 8:1) gave a colorless oil. ^¹H NMR (300 MHz, CDCl₃): δ = 1.50 (d, J = 6.9 Hz, 3 H), 3.75 (s, 3 H), 4.64 (q, J = 6.9 Hz, 1 H), 6.82 (d, J = 8.7 Hz, 2 H), 7.20 (d, J = 8.7 Hz, 2 H), 7.33-7.41 (m, 2 H), 7.42-7.51 (m, 1 H), 7.90-7.98 (m, 2 H). ^¹³C NMR (75 MHz, CDCl₃): δ = 19.5, 46.9, 55.2, 114.4, 128.4, 128.7, 128.8, 132.7, 133.5, 136.5, 158.5, 200.5.