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Synlett 2005(11): 1775-1778  
DOI: 10.1055/s-2005-871540
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© Georg Thieme Verlag Stuttgart · New York

Controlled Monoarylation of Dibromoarenes in Water with a Polymeric Palladium Catalyst

Yasuhiro Uozumi*, Makoto Kikuchi
Institute for Molecular Science, Higashiyama 5-1, Myodaiji, Okazaki 444-8787, Japan
Fax: +81(564)595574; e-Mail: uo@ims.ac.jp;
Further Information

Publication History

Received 19 April 2005
Publication Date:
14 June 2005 (online)

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Abstract

A highly selective monoarylation of dibromoarenes was performed via the Suzuki-Miyaura cross-coupling with arylboronic acids with an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin-supported phosphine-palladium complex in water ­under heterogeneous conditions to give bromobiaryls in high yields. Introduction of two different aryl groups on a aromatic moiety was achieved in a one-pot reaction by successive addition of two kinds of arylboronic acids under similar conditions. The polymeric ­palladium catalyst can be readily recovered and recycled.

Key words

Suzuki-Miyaura coupling - cross-coupling - biaryl ­formation - dibromoarenes

1

Present address: Graduate school of Engineering, Nagoya University, Nagoya, Japan.

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The σ/σ+ value of bromo and phenyl groups: σµ/σµ + (Br) = +0.391/+0.405; σπ/σπ + (Br) = +0.232/+0.150; σµ/σµ + (Ph) = +0.06/+0.109; σπ/σπ + (Ph) = +0.01/-0.179.

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Argo Gel NH2 (Φ = 130 mm, loading value = 0.3 mmol/g) was used as a polymer support.

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General Procedure for Monoarylation of Dibromoarenes.
A mixture of the dibromoarene 1 (0.4 mmol), the arylboronic acid 2 (0.4 mmol), 1 mol% palladium of 5 (4 µmol Pd), 8.4 mg of PPh3 (32 µmol), and 40 µL of toluene in 4 mL of 2 M aqueous solution of K2CO3 was refluxed for 24 h. After being cooled, the mixture was filtered and collected resin beads were extracted with EtOAc. The GC yield and the ratio of 3:4 were determined by GC-MS analysis (internal standard: biphenyl) of the organic extract, and an analytically pure product was isolated by silica gel chromatography.

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During the reaction, generation of precipitates on the resin surface was observed microscopically.

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CAS Registry numbers of biaryl products: 3aA, 844856-52-6; 3aB, 844856-54-8; 3aD, 337535-27-0; 3bC, 251320-87-3; 3cC, 106475-19-8; 3iA, 675590-28-0.

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3-Bromo-2′-methylbiphenyl (3aC). Compound 3aC was not isolated as an analytically pure sample. Characterization of 3aC was performed by GC-MS analysis: MS: m/z = 248, 246 [M+], 167 [M - Br] (base peak), 152, 139, 115, 82.

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1-(3′-Bromobiphen-3-yl)ethanone (3aE). 1H NMR (400 MHz, CDCl3): δ = 8.12 (s, 1 H), 7.94 (d, J = 6.8 Hz, 1 H), 7.73 (d, J = 8.0 Hz, 2 H), 7.48-7.55 (m, 3 H), 7.31 (t, J = 8.0 Hz, 1 H), 2.65 (s, 3H). 13C NMR (100 MHz, CDCl3): δ = 197.4, 142.0, 139.9, 137.4, 131.4, 130.5, 130.2, 130.0, 129.0, 127.6, 126.6, 125.6, 122.8, 26.8. MS: 274, 259, 231, 152, 76.

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1-(4′-Bromobiphen-3-yl)ethanone (3cE). Compund 3cE was not isolated as an analytically pure sample. Characterization of 3cE was performed by GC-MS analysis: MS: m/z = 276, 274 [M+], 261, 259 [M - CH3], 233, 231 [M - COCH3], 152 [M - COCH3-Br] (base peak), 126, 76.

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4-Bromo-2,5,4′-trimethylbiphenyl (3dA).
1H NMR (400 MHz, CDCl3): δ = 7.42 (s, 1 H), 7.20 (d, J = 8.0 Hz, 2 H), 7.15 (d, J = 8.0 Hz, 2 H), 7.06 (s, 1H), 2.38 (s, 3 H), 2.36 (s, 3 H), 2.19 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 140.8, 137.7, 136.5, 134.7, 134.5, 133.5, 133.4, 131.9 (2 C), 128.7 (2 C), 123.1, 22.4, 21.3, 19.8. MS: m/z = 274, 195, 180, 165, 89.

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1-Bromo-4-(4-methylphenyl)naphthalene (3eA). 1H NMR (400 MHz, CDCl3): δ = 8.31 (d, J = 8.4 Hz, 1 H), 7.89 (d, J = 8.4 Hz, 1 H), 7.79 (d, J = 7.6 Hz, 1 H), 7.57 (t, J = 6.8 Hz, 1 H), 7.44 (t, J = 6.8 Hz, 1 H), 7.32 (d, J = 8.0 Hz, 2 H), 7.27 (d, J = 8.4 Hz, 2 H), 7.22 (d, J = 7.6 Hz, 1 H), 2.43 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 140.2, 137.1, 136.8, 132.8, 131.9, 129.7, 129.3, 128.9, 127.3, 127.0 (2 C), 126.6, 126.5, 121.9, 21.4. MS: m/z = 296, 215, 202, 189, 107, 94.

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3-Bromo-5-fluoro-4′-methylbiphenyl (3fA). 1H NMR (400 MHz, CDCl3): δ = 7.49-7.50 (m, 1 H), 7.41 (d, J = 8.0 Hz, 2 H), 7.24 (d, J = 8.0 Hz, 2 H), 7.16-7.21 (m, 2 H), 3.14 (s, 3 H). 13C NMR (100 MHz, CDCl3): δ = 164.0, 161.5, 144.7, 144.6, 138.3, 135.6 (2 C), 130.0, 126.8, 125.8, 125.7, 122.8, 122.7, 117.3, 117.1, 112.8, 112.6, 21.2. MS: m/z = 264, 183, 165, 91.

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3,5-Dibromo-4′-methylbiphenyl (3gA). 1H NMR (500 MHz, CDCl3): δ = 7.58-7.61 (m, 3 H), 7.38-7.40 (m, 2 H), 7.21-7.24 (m, 2 H), 2.38 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 144.5, 138.2, 135.2, 123.0, 129.5, 128.5, 126.7, 123.0, 21.3. MS: m/z = 326, 245, 165, 139, 115, 82.

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2-Bromo-6-(4-methylphenyl)pyridine (3hA). 1H NMR (500 MHz, CDCl3): δ = 7.88 (d, J = 8.5 Hz, 2 H), 7.64 (d, J = 7.0 Hz, 1 H), 7.55 (t, J = 7.5 Hz, 1 H), 7.36 (d, J = 8.0 Hz, 1 H), 7.26 (d, J = 8.5 Hz, 2 H), 2.40 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 158.4, 141.9, 139.5, 138.6, 134.7, 129.3 (2 C), 126.7 (2 C), 125.7, 118.4, 21.5. MS: m/z = 247, 168, 153, 141, 115, 83.

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3-Methoxy-4′′-methyl[1,1′:3′,1′′]terphenyl(6). 1H NMR (500 MHz, CDCl3): δ = 7.77 (br s, 1 H), 7.51-7.54 (m, 4 H), 7.45 (t, J = 7.5 Hz, 1 H), 7.34 (t, J = 7.5 Hz, 1 H), 7.20-7.24 (m, 3 H), 7.16 (t, J = 2.0 Hz, 1 H), 6.89 (dd, J = 7.5, 2.0 Hz, 1 H), 3.81 (s, 3 H), 2.37 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 159.7, 142.6, 141.4 (2 C), 138.0, 136.9, 129.5, 129.3, 128.9, 126.9 (2 C), 125.8, 125.7, 125.6, 119.6 (2 C), 112.9, 112.6, 55.3, 21.2. MS: m/z = 274, 215, 137, 115, 101.

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2-(3-Methoxyphenyl)-6-(4-methylphenyl)pyridine(7). 1H NMR (500 MHz, CDCl3): δ = 8.03 (d, J = 8.0 Hz, 2 H), 7.76 (t, J = 2.5 Hz, 1 H), 7.70 (t, J = 8.0 Hz, 1 H), 7.67 (br d, J = 8.0 Hz, 1 H), 7.59 (t, J = 7.5 Hz, 2 H), 7.37 (t, J = 8.0 Hz, 1 H), 7.26 (d, J = 8.0 Hz, 2 H), 6.95 (dd, J = 7.5, 2.5 Hz, 1 H), 3.86 (s, 3 H), 2.38 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 159.7, 156.4, 156.1, 140.8, 138.6, 137.0, 136.4, 129.3, 129.1, 126.6, 119.2, 118.2, 114.4, 112.5, 55.3, 21.4. MS: m/z = 274, 245, 137.