SCIENCE CHINA Efficient and ligand free palladium catalyst for ...

SCIENCE CHINA Chemistry • SUPPORTING INFORMATION •

doi: 10.1007/s11426-014-5111-1

Efficient and ligand free palladium catalyst for Suzuki and Heck cross-coupling reactions LUO Bin, WANG JiaQing, GE DanHua, LI XinMing, CAO XueQin, PAN Yue & GU HongWei* Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China Received February 17, 2014; accepted March 11, 2014; published online June 23, 2014

General information

General Procedure for the Heck reaction

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H NMR spectra were recorded on a Varian INOVA 400 and and 13C NMR were recorded on a Varian INOVA 100 MHz spectrometer using CDCl3, CD3OD or D6-DMSO as solvent and TMS as internal standard. The resultant product mixtures were analyzed by using a GC (VARIAN CP-3800 GC, HP-5 capillary column, FID detector). General procedure for the Suzuki-Miyaura reaction

A round bottom flask was charged with aryl bromide or chloride (1 mmol), arylboronic acid (1.2 mmol), KOH (2 mmol), Pd(acac)2 (2–3 mg), ethanol or DMF (2 mL) and the mixture was heated and stirred for the times at appropriate temperature. The resultant product mixtures were analyzed by using a GC. The reaction mixture was extracted with ethyl acetate and water, and the corresponding organic layers were dried by evaporation under reduced pressure to obtain the products. The pure products were obtained after purification of the residue by column chromatography on silica gel using corresponding eluents.

A round bottom flask was charged with aryl bromide (1 mmol), styrene (1 mmol), K2CO3 (2 mmol), Pd(acac)2 (2–3 mg), DMF (2 mL) and the mixture was heated and stirred for the times at appropriate temperature. The resultant product mixtures were analyzed by using a GC. The reaction mixture was extracted with ethyl acetate and water, and the corresponding organic layers were dried by evaporation under reduced pressure to obtain the products. The pure products were obtained after purification of the residue by column chromatography on silica gel using corresponding eluents. Spectral data for compounds

Biphenyl (1a) 1

H NMR (400 MHz, DMSO-d6): δ = 6.83–6.77 (m, 4H), 6.64–6.58 (m, 4H), 6.54–6.48 (m, 2H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 140.18, 128.93, 127.42, 126.69 ppm.

4-Methylbiphenyl (1b) *Corresponding author (email: [email protected]) © Science China Press and Springer-Verlag Berlin Heidelberg 2014

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September (2014) Vol.57 No.9

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H NMR (400 MHz, DMSO-d6): δ = 7.62 (t, J = 7.8 Hz, 2H), 7.54 (t, J = 8.2 Hz, 2H), 7.47–7.41 (m, 2H), 7.36–7.30 (m, 1H), 7.26 (t, J = 6.9 Hz, 2H), 2.34 (s, 3H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 140.45, 137.65, 137.04, 129.86, 129.21, 127.44, 21.07 ppm.

4-Methoxybiphenyl (1c)

4-Nitro-biphenyl (1h) 1

H NMR (400 MHz, DMSO-d6): δ = 8.31 (d, J = 8.9 Hz, 2H), 7.97 (t, J = 8.9 Hz, 2H), 7.79 (t, J = 7.2 Hz, 2H), 7.57–7.47 (m, 3H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 146.64, 137.83, 129.27, 129.10, 127.87, 127.30, 124.12 ppm.

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H NMR (400 MHz, DMSO-d6): δ = 7.63–7.57 (m, 4H), 7.43 (t, J = 7.3 Hz, 2H), 7.30 (t, J = 7.2 Hz, 1H), 7.02 (d, J = 8.2 Hz, 2H), 3.79 (s, 3H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 159.09, 140.79, 133.73, 128.70, 128.13, 126.71, 126.63, 114.16, 55.32 ppm.

1-Biphenyl-4-yl-ethanone (1d)

4'-Methoxy-4-methyl-biphenyl (1i) 1

H NMR (400 MHz, CDCl3): δ = 7.51 (d, J = 8.5 Hz, 2H), 7.45 (d, J = 7.8 Hz, 2H), 7.23 (d, J = 7.6 Hz, 2H), 6.97 (d, J = 8.4 Hz, 2H), 3.85 (s, 3H), 2.39 (s, 3H) ppm; 13C NMR (100 MHz, CDCl3): δ = 155.51, 146.77, 136.49, 132.62, 129.57, 128.98, 128.09, 126.72, 114.27, 55.48, 21.21 ppm.

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H NMR (400 MHz, CDCl3): δ = 8.04 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H), 7.63 (d, J = 7.2 Hz, 2H), 7.48 (t, J = 7.4 Hz, 2H), 7.41 (t, J = 7.3 Hz, 1H), 2.64 (s, 3H) ppm; 13 C NMR (100 MHz, CDCl3): δ = 197.81, 145.78, 139.87, 135.85, 129.02, 128.98, 128.30, 127.32, 127.26, 26.75 ppm.

4,4'-Dimethyl-biphenyl (1j) 1

H NMR (400 MHz, DMSO-d6): δ = 7.52 (d, J = 8.1 Hz, 4H), 7.24 (d, J = 8.0 Hz, 4H), 2.33 (s, 6H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 137.22, 136.34, 129.48, 126.25, 20.67 ppm.

Biphenyl-4-carbaldehyde (1e) 1

H NMR (400 MHz, DMSO-d6): δ = 9.17 (s, 1H), 7.11 (d, J = 8.1 Hz, 2H), 7.02 (d, J = 8.0 Hz, 2H), 6.88 (d, J = 7.2 Hz, 2H), 6.63 (t, J = 7.3 Hz, 2H), 6.57 (t, J = 7.2 Hz, 1H) ppm; 13 C NMR (100 MHz, DMSO-d6): δ = 191.00, 144.18, 137.10, 133.38, 128.47, 127.43, 126.90, 125.66, 125.43 ppm.

Biphenyl-4-carbonitrile (1f)

Biphenyl-2-ylamine (1k) 1

H NMR (400 MHz, DMSO-d6): δ = 6.64–6.44 (m, 5H), 6.22–6.09 (m, 2H), 5.91 (d, J = 8.0 Hz, 1H), 5.77 (t, J = 7.4 Hz, 1H), 3.88 (s, 2H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 144.93, 139.69, 130.03, 128.74, 128.64, 128.18, 126.75, 125.78, 116.78, 115.25 ppm.

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H NMR (400 MHz, DMSO-d6): δ = 7.94–7.87 (m, 4H), 7.75 (d, J = 7.8 Hz, 2H), 7.54–7.43 (m, 3H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 144.64, 138.26, 132.86, 129.18, 128.77, 127.58, 127.09, 118.09, 110.05 ppm.

3-Methyl-biphenyl (1l) 1

4-Trifluoromethyl-biphenyl (1g) 1

H NMR (400 MHz, DMSO-d6): δ = 7.01 (d, J = 8.1 Hz, 2H), 6.93 (d, J = 8.1 Hz, 2H), 6.86 (d, J = 7.8 Hz, 2H), 6.65(t, J = 7.3 Hz, 2H), 6.61–6.55 (m, 1H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 139.80, 134.23, 124.75, 124.55, 124.07, 123.10, 122.67, 122.32, 121.36, 26.28 ppm.

H NMR (400 MHz, CD3OD): δ = 7.48 (d, J = 6.2 Hz, 2H), 7.32–7.22 (m, 6H), 7.05 (d, J = 5.6 Hz, 1H), 2.28 (s, 3H) ppm; 13C NMR (100 MHz, CD3OD): δ = 142.00, 141.83, 138.82, 129.21, 128.45, 128.15, 127.61, 127.48, 124.63, 21.20 ppm.

2-Nitro-biphenyl (1m)

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H NMR (400 MHz, DMSO-d6): δ = 7.98 (d, J = 8.1 Hz, 1H), 7.76 (t, J = 7.6 Hz, 1H), 7.63 (t, J = 7.8 Hz, 1H), 7.56 (d, J = 7.7 Hz, 1H), 7.49–7.42 (m, 3H), 7.34 (d, J = 8.0 Hz, 2H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 147.00, 134.99, 133.08, 130.94, 129.88, 126.84, 126.29, 125.81, 122.09 ppm.

(E)-Stilbenze (2a)

4-Styryl-benzaldehyde (2c) 1

H NMR (400 MHz, DMSO-d6): δ = 9.15 (s, 1H), 7.08 (d, J = 8.2 Hz, 2H), 6.99 (d, J = 8.1 Hz, 2H), 6.83 (d, J = 7.9 Hz, 2H), 6.64 (s, 1H), 6.60–6.55 (m, 3H), 6.52–6.47 (m, 2H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 192.39, 143.11, 135.10, 131.96, 130.02, 128.81, 128.41, 127.29, 127.00, 126.95 ppm.

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H NMR (400 MHz, DMSO-d6): δ = 6.73 (d, J = 7.4 Hz, 4H), 6.50 (t, J = 7.6 Hz, 4H), 6.44–6.36 (m, 4H) ppm; 13C NMR (100 MHz, DMSO-d6): δ = 136.88, 128.59, 128.27, 127.54, 126.37 ppm. 1-Nitro-4-styryl-benzene (2d) 1

1-Methoxy-4-styryl-benzene (2b) 1

H NMR (400 MHz, DMSO-d6): δ = 7.55 (t, J = 7.2 Hz, 4H), 7.36 (t, J = 7.6 Hz, 2H), 7.26–7.21 (m, 1H), 7.18 (s, 1H), 7.11 (s, 1H), 6.94 (d, J = 8.7 Hz, 2H), 3.77 (s, 3H) ppm; 13 C NMR (100 MHz, DMSO-d6): δ = 137.38, 129.65, 128.67, 128.05, 127.80, 127.18, 126.16, 114.17, 55.16 ppm.

H NMR (400 MHz, DMSO-d6); δ = 8.24 (d, J = 8.2 Hz, 2H), 7.87 (d, J = 8.3 Hz, 2H), 7.68 (d, J = 7.8 Hz, 2H), 7.53 (s, 1H), 7.46–7.40 (m, 3H), 7.35 (d, J = 8.1 Hz, 1H) ppm; 13 C NMR (100 MHz, DMSO-d6): δ = 144.05, 136.31, 133.28, 128.90, 128.76, 127.35, 127.17, 126.40, 124.09 ppm.

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The 1H NMR and 13C NMR charts of products Biphenyl (1a)


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4-Methylbiphenyl (1b)

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4-Methoxybiphenyl (1c)

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1-Biphenyl-4-yl-ethanone (1d)

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Biphenyl-4-carbaldehyde (1e)

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Biphenyl-4-carbonitrile (1f)

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4-Trifluoromethyl-biphenyl (1g)

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4-Nitro-biphenyl (1h)

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4'-Methoxy-4-methyl-biphenyl (1i)

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4,4'-Dimethyl-biphenyl (1j)

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Biphenyl-2-ylamine (1k)

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3-Methyl-biphenyl (1l)

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2-Nitro-biphenyl (1m)

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(E)-Stilbenze (2a)

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1-Methoxy-4-styryl-benzene (2b)

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4-Styryl-benzaldehyde (2c)

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1-Nitro-4-styryl-benzene (2d)

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Reaction conditions: 2 mg Pd(acac)2, 10 mmol 1-bromo-4-methoxybenzene, 12 mmol phenylboronic acid, 20 mmol base and 20 mL ethanol, 5 min at 70 °C under nitrogen

Entry 1 a) Conversion to the coupled product determined by GC.

Time (min) 5

Yield a)(%) 90

Reaction conditions: 2.5 mg catalyst, 1 mmol 1-bromo-4-methoxybenzene, 1.2 mmol phenylboronic acid, 2 mmol base and 2mL ethanol, 5 min at 70 °C under nitrogen

Entry 1 2 3 a) Conversion to the coupled product determined by GC.

Catalyst Pd(acac)2 PdCl2 Pd(OAc)2

Yield a)(%) 94 53 69