Efficient PdCl2–catalyzed Suzuki reactions using simple dicationic imidazolium salts as
ligands in aqueous DMF
Qing Huang ·· Jiabin Qiu · Limei Li · Guohai Xu · Zhonggao Zhou
Experimental
General considerations
Materials and methods
All chemicals employed in the synthesis were obtained commercially, and used as received
without further purification. NMR spectra were recorded on a Bruker Avance III 400 MHz
spectrometer. GC–MS analyses were carried out on an Agilent 6890 GC with 5973 mass
detector. The dicationic imidazolium salts 1, 2, and 3 were prepared by following the literature
method.[1]
GC-MS analysis
All of the experiments were carried out on an agilent 6890 GC with 5973 mass spectral
detector, using an AT.SE-30 column of 50 m length, 0.32 mm diameter and 0.5 μm film
thicknesses. GC parameters for Suzuki reactions were as follows: injector temperature 280 ◦C;
detector temperature 280 ◦C; initial temperature 100 ◦C; initial time 5 min; temperature ramp 1,
30 ◦C min−1; final temperature 200 ◦C; ramp 2, 20 ◦C min−1; final temperature 250 ◦C; run time
30 min; inject 1.0 μL; helium as the GC carrier gas; pressure of the system was 3.5 bar.
*
College of Chemistry and Chemical Engineering, Gannan Normal University, Ganzhou 341000, P. R. China
E-mail: zhgzhou@foxmail.com (Z.-G. Zhou)
General procedure for the Suzuki reactions
The appropriate amounts of the required dicationic imidazolium ligand, base (2.0 equivalents)
and Pd metal precursor were added to 1,4-dioxane. The mixture was stirred at 60 oC for 30
min under nitrogen, after which the palladium catalyst was formed in situ. The 1,4-dioxane was
then removed under reduced pressure and the required solvent, aryl halide (1.0 equivalent),
aryl boronic acid (1.5 equivalent), and decane (internal standard) were added. The reaction
was monitored by GC–MS, and the GC yields were calculated against the added decane. On
completion of the reaction, the residue was extracted with ether (3 × 3.0 mL) and the organic
solvent was evaporated under reduced pressure. The crude product was purified by column
chromatography, and the products were characterized by 1H and 13C NMR spectra. The crude
product was purified by column chromatography, and the products were characterized by 1H,
13C NMR spectra and the datas could be found in following.
4a
(1)
4-Methyl-1,1'-biphenyl (Table 3, entries 1, 2 and 9),[2]
1H
NMR (400 MHz, CDCl3): δ 7.58 (d, J = 7.6 Hz, 2 H, Ar-H), 7.50 (d, J = 8.4 Hz, 2 H, Ar-H),
7.44 (t, J = 7.2 Hz, 2 H, Ar-H), 7.33 (t, J = 6.8 Hz, 1 H, Ar-H), 7.25 (t, J = 3.2 Hz, 2 H, Ar-H),
2.41 (s, 3 H, CH3) ppm.
4b
(2)
[1,1'-biphenyl]-4-carbonitrile (Table 3, entry 3)[3]
1H
NMR (400 MHz, CDCl3): δ 7.53–7.64 (m, 4 H , Ar-H), 7.50 (d, 2 H, J = 7.8 Hz, Ar-H),
7.35–7.42 (m, 3 H, Ar-H), ppm.
(3)
4c
4-Methoxy-1,1'-biphenyl (Table 3, entry 4),[4]
1H
NMR (400 MHz, CDCl3): δ 7.54 (t, J = 8.0 Hz, 4 H, Ar-H), 7.42 (t, J = 7.6 Hz, 2 H, Ar-H),
7.31 (d, J = 7.2 Hz, 1 H, Ar-H), 6.98 (d, J = 8.8 Hz, 2 H, Ar-H), 3.86 (s, 3 H, OCH3) ppm.
(4)
4d
1-([1,1'-biphenyl]-4-yl)ethanone (Table 3, entry 5),[2]
1H
NMR (400 MHz, CDCl3): δ 8.19 (d, J = 7.6 Hz, 1 H, Ar-H), 7.97 (d, J = 8.0 Hz, 2 H, Ar-H),
7.33~7.63 (m, 5 H, Ar-H), 7.18 (s, 1 H, Ar-H), 2.57 (s, 3 H, CH3) ppm.
(5)
4e
2-Methyl-1,1'-biphenyl (Table 3, entry 6),[5]
1H
NMR (400 MHz, CDCl3): δ 7.39-7.43 (m, 2 H, Ar-H), 7.31-7.35 (m, 3 H, Ar-H), 7.24-7.26 (m,
4 H, Ar-H), 2.25 (s, 3 H, CH3) ppm.
(6)
4f
Biphenyl (Table 3, entry 7),[6]
1H
NMR (400 MHz, CDCl3, TMS) δ 7.60 (d, 4 H, J = 7.5 Hz), 7.44 (t, 4 H, J = 7.2 Hz), 7.35 (t, 2
H, J = 7.2 Hz) ppm.
4g
(7)
2-methoxy-1,1'-biphenyl (Table 3, entry 8)[7]
1H NMR (400 MHz, CDCl3): δ 7.58–7.56 (m, 2H, Ar-H), 7.43–7.39 (m, 2H, Ar-H), 7.35–7.31(m,
2H, Ar-H), 7.17–7.12 (m, 2H, Ar-H), 6.87 (dd, J = 8.4 and 2.4 Hz, 1H, Ar-H), 3.82 (s, 3H, CH3),
ppm.
(8)
4h
4-(trifluoromethyl)-1,1'-biphenyl (Table 3, entry 10),[8]
1H
NMR (400 MHz, CDCl3): δ 7.33 (t, J = 7.2 Hz, 1 H, Ar-H), 7.40 (t, J = 7.4 Hz, 2 H, Ar-H),
7.54 (d, J = 6.8 Hz, 2 H, Ar-H), 7.62 (s, 4 H, Ar-H) ppm.
4i
(9)
1-(3',4',5'-trifluoro-[1,1'-biphenyl]-4-yl)ethanone (Figure 1),[5]
1H
NMR (400 MHz, CDCl3): δ 8.04 (d, 2 H, J = 8.0 Hz, Ar-H), 7.60 (d, 2 H, J = 8.0 Hz, Ar-H),
7.24 (m, 2 H, Ar-H), 2.65 (s, 3 H, CH3 ), ppm.
13C
NMR (100 MHz, CDCl3, δ): 197.41, 151.52,
142.47, 139.79, 136.72, 135.97, 129.12, 127.03, 111.42, 111.26, 26.69, ppm.
4j
(10)
1-(3',5'-difluoro-[1,1'-biphenyl]-4-yl)ethanone (Figure 1),[9]
1H
NMR (400 MHz, CDCl3): δ 8.03 (d, 2 H, J = 8.0 Hz, Ar-H), 7.62 (d, 2 H, J = 8.0 Hz, Ar-H),
7.11 (m, 2 H, Ar-H), 6.82 (m, 2 H, Ar-H), 2.64 (s, 3 H, CH3 ), ppm. 13C NMR (100 MHz, CDCl3,
δ): 197.45, 164.56, 162.08, 143.37, 143.11, 136.76, 129.04, 127.16, 110.24, 110.05, 103.41,
26.65 ppm.
(11)
4k
1-(4'-methyl-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[10]
1H
NMR (400 MHz, CDCl3): δ8.02 (d, J = 8.0 Hz, 2 H, Ar-H) 7.67 (d, J = 8.0 Hz, 2 H, Ar-H),
7.53 (d, J =8.0 Hz, 2 H, Ar-H), 7.28 (d, J = 8.0 Hz, 2 H, Ar-H), 2.63 (s, 3 H, CH3), 2.41 (s, 3 H,
CH3), ppm.
13C
NMR (100 MHz, CDCl3) δ 197.5, 141.1, 140.2, 135.6, 129.1, 126.8, 126.4,
126.2, 122.1, 26.6 ppm.
4l
(12)
1-(4'-(hydroxymethyl)-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[11]
1H
NMR (400 MHz, CDCl3): δ 8.02 (d, 2 H, J = 8.0 Hz, Ar-H), 7.68 (d, 4 H, J = 8.0 Hz, Ar-H),
7.47 (d, 2 H, J = 8.0 Hz, Ar-H), 4.76 (s, 2 H, CH2), 2.64 (s, 2 H, CH3) ppm.
13C
NMR (101 MHz, CDCl3) δ 197.71, 145.39, 141.00, 139.21, 135.91, 128.93, 127.52, 127.43,
127.13, 64.93, 26.61 ppm
(13)
4m
1-(4'-fluoro-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[12]
1H
NMR (400 MHz, CDCl3): δ 8.03 (d, 2 H, J = 8.0 Hz, Ar-H), 7.60 (m, 4 H, Ar-H), 7.16 (t, 2 H, J
= 12.0 Hz, Ar-H), 2.64 (s, 3 H, CH3) ppm.
NMR (100 MHz, CDCl3): δ197.70, 164.24,
13C
161.78, 144.75, 135.99, 135.84, 128.99, 128.90, 127.08, 116.04, 115.83, 26.79 ppm.
(14)
4n
1-(4'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl)ethanone (Figure 1).[13]
1H
NMR (400 MHz, CDCl3): δ 8.06 (d, 2 H, J = 8.0 Hz, Ar-H), 7.73 (s, 2 H, Ar-H), 7.68 (d, 2 H, J
= 8.0 Hz, Ar-H), 2.65 (s, 3 H, CH3), ppm.
13C
NMR (100 MHz, CDCl3): δ 197.50, 144.10,
143.37, 136.61, 130.20, 129.02, 127.58, 127.42, 125.87, 125.48, 122.77, 26.61 ppm.
(15)
4o
4'-acetyl-[1,1'-biphenyl]-4-carbonitrile (Figure 1)[14]
1H
NMR (400 MHz, CDCl3): δ 8.07(d, 2 H, J = 8.0 Hz, Ar-H), 7.75 (m, 4 H, Ar-H), 7.69 (d, 2 H, J
= 8.0 Hz, Ar-H), 2.65 (s, 3 H, CH3), ppm. 13C NMR (100 MHz, CDCl3): δ197.47, 144.27, 143.48,
136.89, 132.73, 129.12, 127.93, 127.45, 118.65, 111.86, 26.73. ppm.
(16)
4p
1-(4'-phenoxy-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[15]
1H
NMR (400 MHz, CDCl3, TMS) δ 8.01 (d, J = 8.0 Hz, 2 H, Ar-H), 7.65 (d, J = 8.0 Hz, 2 H,
Ar-H), 7.59 (d, J = 8.0 Hz, 2 H, Ar-H), 7.37 (t, J = 8.0 Hz, 4 H, Ar-H), 7.14 (t, J = 8.0 Hz, 1 H,
Ar-H), 7.05 (t, J = 8.0 Hz, 4 H, Ar-H), 2.63 (s, 3 H, CH3); 13C NMR (100 MHz, CDCl3, δ): 197.64,
157.84, 156.79, 145.09, 135.67, 134.69, 129.87, 128.97, 128.61, 126.87, 123.70, 119.28,
118.98, 26.60 ppm.
4q
(17)
Ethyl 4'-acetyl-[1,1'-biphenyl]-4-carboxylate (Figure 1)[12]
1H
NMR (400 MHz, CDCl3, TMS) δ 8.14 (d, J = 8.0 Hz, 2 H, Ar-H), 8.06 (d, J = 8.0 Hz, 2 H,
Ar-H), 7.72 (d, J = 8.0 Hz, 2 H, Ar-H), 7.69 (t, J = 8.0 Hz, 2 H, Ar-H), 4.41 (q, J = 7.2 Hz, 2 H,
CH2), 2.63 (s, 3 H, COCH3), 1.43 (t, J = 7.2 Hz, 2 H, CH3);
13C
NMR (100 MHz, CDCl3, δ):
197.65, 166.30, 144.53, 144.01, 136.48, 130.20, 128.99, 127.45, 127.20, 113.69, 61.14, 26.72,
14.36 ppm.
4r
(18)
1-(4'-(diphenylamino)-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[16]
1H
NMR (400 MHz, CDCl3, TMS) δ 8.00 (d, J = 8.0 Hz, 2 H, Ar-H), 7.65 (d, J = 8.0 Hz, 2 H,
Ar-H), 7.50 (d, J = 8.0 Hz, 2 H, Ar-H), 7.28 (t, J = 8.0 Hz, 4 H, Ar-H), 7.13 (d, J = 8.0 Hz, 6 H,
Ar-H), 7.05 (t, J = 8.0 Hz, 2 H, Ar-H), 2.62 (s, 3 H, CH3); 13C NMR (100 MHz, CDCl3, δ): 197.63,
148.19, 147.43, 145.21, 135.34, 133.14, 129.39, 128.98, 127.93, 126.50, 124.79, 123.37,
123.29, 26.63 ppm.
(19)
4s
1-(3'-(trifluoromethyl)-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)
1H
NMR (400 MHz, CDCl3): δ 8.08 (d, 2 H, J = 8.0 Hz, Ar-H), 7.87 (s, 1 H, Ar-H), 7.80 (d, 1 H, J
= 8.0 Hz, Ar-H), 7.67 (m, 3 H, Ar-H), 7.60 (m, 1 H, Ar-H), 2.66 (s, 3 H, CH3), ppm.
13C
NMR
(100 MHz, CDCl3): δ 197.57, 144.10, 140.67, 136.47, 131.20, 130.55, 129.50, 129.07, 127.32,
124.86, 124.82, 124.02, 26.65 ppm.
4t
(20)
1-([1,1':3',1''-terphenyl]-4-yl)ethanone (Figure 1)[17]
1H
NMR (400 MHz, CDCl3, TMS) δ 8.03 (d, J = 8.0 Hz, 2 H, Ar-H), 7.81 (s, 1 H, Ar-H), 7.71 (d,
J = 8.0 Hz, 2 H, Ar-H), 7.62 (m, 4 H, Ar-H), 7.52 (d, J = 8.0 Hz, 2 H, Ar-H), 7.37 (d, J = 8.0 Hz, 2
H, Ar-H), 2.62 (s, 3 H, CH3); 13C NMR (100 MHz, CDCl3, δ): 197.86, 145.76, 142.075, 140.89,
140.45, 135.99, 129.44, 129.00, 128.92, 127.64, 127.37, 127.28, 127.11, 126.23, 26.707 ppm.
(21)
4u
1-(3'-nitro-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[18]
1H
NMR (400 MHz, CDCl3) δ 8.45 (s, 1 H, Ar-H), 8.23 (d, J = 8.0 Hz, 1 H, Ar-H), 8.07 (d, J = 8.0
Hz, 2 H, Ar-H), 7.95 (d, J = 8.0 Hz,1 H, Ar-H), 7.72 (d, J = 8.0 Hz, 2 H, Ar-H), 7.66 (t, J = 8.0 Hz,
2 H, Ar-H), 2.66 (s, 3 H, CH3) 2.66 ppm. 13C NMR (100 MHz, CDCl3) δ 197.42, 148.73, 142.90,
141.47, 136.83, 133.12, 130.00, 129.16, 127.32, 122.85, 122.01, 77.44, 77.12, 76.80, 26.68
ppm
(22)
4v
1-(4-(benzo[d][1,3]dioxol-5-yl)phenyl)ethanone (Figure 1)[10]
1H
NMR (400 MHz, CDCl3, TMS) δ 7.92 (s, 2 H, Ar-H), 7.53 (s, 2 H, Ar-H), 7.03 (s, 2 H, Ar-H),
6.84 (s, 1 H, Ar-H), 5.95 (s, 2 H, CH3), 2.56 (s, 3 H, CH3) ppm;
13C
NMR (100 MHz, CDCl3) δ
197.70, 148.34, 147.89, 145.36, 135.44, 134.01, 128.93, 126.78, 121.05, 108.73, 107.56,
101.39, 26.64 ppm.
(23)
4w
1-(3',5'-bis(trifluoromethyl)-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[13]
1H
NMR (400 MHz, CDCl3): δ 8.10 (m, 2 H, J = 8.0 Hz, Ar-H), 8.06 (s, 2 H, Ar-H), 7.92 (s, 1 H,
Ar-H), 7.73(m, 2 H, J = 8.0 Hz, Ar-H), 2.68 (s, 3 H, CH3 ), ppm. 13C NMR (100 MHz, CDCl3): δ
197.38, 142.48, 142.04, 137.12, 132.38, 129.26, 127.50, 127.35, 124.57, 121.80, 119.14,
26.74 ppm.
4x
(24)
1-(4-(naphthalen-1-yl)phenyl)ethanone (Figure 1)[19]
1H
NMR (400 MHz, CDCl3): δ 8.00 (d, 2 H, J = 8.0 Hz, Ar-H), 7.83–7.74 (m, 3H, Ar-H),
7.51–7.46 (m, 2H, Ar-H), 7.43–7.36 (m, 2H, Ar-H), 7.33–7.31 (m, 2H, Ar-H), 2.58 (s, 3H, CH3 )
ppm.
13C
NMR (100 MHz, CDCl3): δ 197.8, 145.7, 138.9, 135.9, 133.7, 131.1, 130.3, 128.3,
126.9, 126.3, 125.9, 125.3, 26.7 ppm.
(25)
4y
1-(4-(naphthalen-2-yl)phenyl)ethanone (Figure 1)[20]
1H
NMR (400 MHz, CDCl3) δ 8.07 (m, 3 H, Ar-H), 7.89 (m, 3 H, Ar-H), 7.79 (d, J = 8.0 Hz, 2 H,
Ar-H), 7.74 (d, J = 8.0 Hz, 1 H, Ar-H), 7.51(m, 3 H, Ar-H), 2.64 (s, 3 H, CH3); 13C NMR (100 Hz,
CDCl3) δ 197.74, 145.68, 137.15, 135.89, 133.57, 133.03, 128.99, 128.72, 128.37, 127.70,
127.46, 126.58, 126.50, 126.38, 125.17, 6.68 ppm.
(26)
4z
1-(3',5'-dimethyl-[1,1'-biphenyl]-4-yl)ethanone (Figure 1)[21]
1H
NMR (400 MHz, CDCl3) δ 7.97 (d, J = 8.0 Hz, 2 H, Ar-H), 7.62 (d, J = 8.0 Hz, 2 H, Ar-H),
7.20 (s, 2 H, Ar-H), 7.01 (s, 1 H, Ar-H), 2.59 (s, 3 H, CH3), 2.36 (s, 6 H, CH3); 13C NMR (100 Hz,
CDCl3) δ 197.88, 146.08, 139.83, 138.49, 137.89, 135.69, 129.93, 129.72, 128.86, 127.20,
125.17, 26.60, 21.41 ppm.
Acknowledgments We gratefully thank the financial support from The National Natural
Science Foundation of China (No. 21241005 and 21201040), the Key Laboratory of Jiangxi
University for Functional Materials Chemistry.
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