Room-temperature Kumada cross-coupling of unactivated aryl chlorides catalyzed by N-heterocylic carbene-based nickel(II) complexes

Article abstract of DOI:10.1021/jo800197u

(Chemical Equation Presented) The Kumada cross-coupling reaction of a variety of unactivated aryl chlorides, vinyl chlorides, and heteroaryl chlorides catalyzed by nickel(II) complexes containing pyridine-functionalized NHC ligands is described. The catalysts are so active that the reactions proceed at room temperature in excellent yields.

Full text of DOI:10.1021/jo800197u

Room Temperature Kumada Cross-Coupling of
Unactivated Aryl Chlorides Catalysed by N-Heterocylic
Carbene-Based Nickel(II) Complexes
Zhenxing Xia, Bin Liua, and Wanzhi Chenab*
a Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028, P.
R. China and b Schoole of Chemistry and Chemical Engineering, Liaocheng University,
Liaocheng 252059, P. R. China
chenwzz@zju.edu.cn
Supporting Information
List of Contents
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Figure S1, molecular structure and synthesis of 4
General remarks.
S2-S3
S3
S3
General experimental procedure
Characterization data the products in the coupling reaction.
References.
S3-S12
S12-S13
S14-S48
Spectra.
S1

ꢀ Figure S1, molecular structure and synthesis of 4
Figure S1. Molecular structure of the cation of 4.
Synthesis of complex 4. A solution of 1,1’-di(2-picolyl)-3,3’-ethoxyethyldiimida-
zolium dihexafluorophosphate (680 mg, 1.0 mmol) in 10 mL of CH3CN was treated
with Ag2O (232 mg, 1.0 mmol). The mixture was allowed to react at room temperature
for 10 hours, and then filtered to remove a small amount of unreacted Ag2O. The
filtrate was treated with Ni(PPh3)2Cl2 (654 mg, 1.0 mmol). After it was stirred at room
temperature for another 10 hours, the solution was filtered, and the filtrate was
concentrated to ca. 5 mL. Addition of 20 mL of diethyl ether gave a yellow solid. Yield:
390 mg, 53%. Anal. Calcd for C22H24F12N6NiOP2: C, 35.85; H, 3.28; N, 11.40. Found:
1
C, 35.76; H, 3.64; N, 11.30. H NMR (400 MHz, CD3CN): 8.02 (t, J = 7.6 Hz, 2H),
7.91 (d, J = 4.8 Hz, 2H), 7.79 (d, J = 7.6 Hz, 2H), 7.53 (s, 2H), 7.27 (t, J = 6.4 Hz, 2H),
7.18 (s, 2H), 6.62 (d, J = 15.2 Hz, 2H), 5.61 (d, J = 15.2
S2

13
Hz, 2H), 3.97 (t, J = 12.4 Hz, 4H), 3.61 (m, 2H), 3.48 (m, 2H) ppm. C NMR (400
MHz, CD3CN): 156.3 (Ni-C), 155.3, 153.2, 142.0, 126.2, 126.1, 125.8, 123.8, 70.9,
54.9, 52.1 ppm.
ꢀ General Remarks
All reactions were carried out in Schlenk tubes under an atmosphere of N2, Organic
solvents were dried over 4 Å molecular sieves before being used. 1,1’-Di(2-picolyl)-
2
3,3’-ethoxyethyldiimidazolium dihexafluorophosphate1, Ni(PPh3)2Cl2 , NHC nickel
complexes 13, 24 and 33 were prepared according to the known procedure. Chemical
shifts (δ) are expressed in ppm downfield to TMS at δ = 0 ppm and coupling constants
(J) are expressed in Hz.
ꢀ General Experimental Procedure
An oven-dried Schlenk tube equipped with a Teflon valve was charged with a
magnetic stir bar, NHC nickel catalyst. The tube was evacuated and backfilled with N2
(this procedure was repeated three times). Then added the anhydrous THF 3 mL to the
tube. To the solution formed was added dropwise a solution of p-C6H5MgBr in THF
( 1.2 mmol, 1 M THF ) at room temperature with stirring. The stirring was continued at
room temperature for 12 hours. The reaction was ceased by addition of water. The
mixture was extracted with ethyl acetate ( 3 ×5 mL ). The combined organic layers
were dried by MgSO4. The MgSO4 was removed by filtration and washed by ethyl
acetate. The resulting ethyl acetate solution was concentrated by rotary evaporation
and the crude product was purified by column chromatograph on sillca gel (petroleum
ether) to afford the desired product.
ꢀ Characterization data of the products in the coupling reaction.
S3

(1)
Me
4-methylbiphenyl (Table 1, entry 1) 5
1H NMR (400 MHz, CDCl3, TMS): δ 7.57 (d, J = 8.0 Hz, 2H), 7.49 (d, J = 8.0
Hz, 2H), 7.43 (t, J = 7.6 Hz, 2H), 7.32 (t, J = 7.6 Hz, 1H), 7.24 (t, J = 7.6 Hz, 2H),
2.38 (s, 3H) ppm. MS (EI, m/z): 168 [M+].
(2)
Me
N
2-p-tolylpyridine (Table 1, entry 6) 6
1H NMR (400 MHz, CDCl3, TMS): δ 8.66 (d, J = 4.4 Hz, 1H), 7.89 (d, J = 8.0 Hz,
2H), 7.70 (m, 2H), 7.28 (d, J = 8.0 Hz, 2H), 7.17 (m, 1H), 2.39 (s, 3H) ppm. MS
(EI, m/z): 169 [M+].
(3)
Me
OMe
4-methoxy-4'-methylbiphenyl (Table 1, entry 7) 7
1H NMR (400 MHz, CDCl3, TMS): δ 7.51 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz,
2H), 7.24 (m, 2H), 6.97 (d, J = 8.8 Hz, 2H), 3.84 (s, 3H), 2.37 (s, 3H) ppm. MS
(EI, m/z): 199 [M+]
(4)
N
Me
N
2-p-tolylpyrimidine (2a) 8
1H NMR (400 MHz, CDCl3, TMS): δ 8.78 (d, J = 4.8 Hz, 2H), 8.34 (d, J = 8.0 Hz,
2H), 7.31 (d, J = 8.0 Hz, 2H), 7.15(d, J = 4.8 Hz, 1H), 2.42 (s, 3H) ppm. MS
S4

(EI, m/z): 170 [M+]
(5)
Me
Me
N
N
Me
2,4-dimethyl-7-p-tolyl-1,8-naphthyridine (2b)
1H NMR (400 MHz, CDCl3, TMS): δ 8.34 (d, J = 8.4 Hz, 1H), 8.25 (d, J = 8.0 Hz,
2H), 7.93 (d, J = 8.4 Hz, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.16 (s, 1H), 2.77 (s, 3H),
2.67 (s, 3H), 2.43 (s, 3H) ppm. 13C NMR (100 MHz, CDCl3, TMS): δ 162.8,
159.4, 155.9, 145.0, 143.6, 139.9, 135.7, 133.6, 132.0, 129.4, 127.6, 122.9, 119.5,
118.0, 25.5, 21.3, 17.9 ppm. HRMS (ESI) m/e Calcd (M++Na) 271.1206, Found
271.1206. MS (EI, m/z): 248 [M+]
(6)
F3C
Me
4-methyl-4'-(trifluoromethyl)biphenyl (2c) 9
1H NMR (400 MHz, CDCl3, TMS): δ 7.67 (s, 4H), 7.50 (d, J = 7.6 Hz, 2H), 7.28 (d,
J = 7.6 Hz, 2H), 2.41 (s, 3H) ppm. MS (EI, m/z): 236 [M+]
(7)
Me
CN
4'-methylbiphenyl-2-carbonitrile (2d) 10
1H NMR (400 MHz, CDCl3, TMS): δ 7.75 (d, J = 7.6 Hz, 1H), 7.61 (m, 1H), 7.50
(m, 4H), 7.30 (m, 1H) ppm. MS (EI, m/z): 193 [M+]
(8)
S5

NC
Me
4'-methylbiphenyl-4-carbonitrile (2e) 31
1H NMR (400 MHz, CDCl3, TMS): δ 7.71 (2d, J = 8.4, 17.2 Hz, 4H), 7.49 (d, J =
8.0 Hz, 2H), 7.29 (d, J = 8.0 Hz, 2H), 2.41 (s, 3H) ppm. MS (EI, m/z): 193 [M+]
(9)
Me
NC
4'-methylbiphenyl-3-carbonitrile (2f) 31
1H NMR (400 MHz, CDCl3, TMS): δ 7.84 (s, 1H), 7.79 (d, J = 7.6 Hz, 1H), 7.60
(d, J = 8.0 Hz, 1H), 7.53 (t, J = 8.0 Hz, 1H), 7.46 (d, J = 8.0 Hz, 2H), 7.29 (d, J =
8.0 Hz, 2H), 2.40 (s, 3H) ppm. MS (EI, m/z): 193 [M+]
(10)
Me
Me
2,4'-dimethylbiphenyl (2g) 11
1H NMR (400 MHz, CDCl3, TMS): δ 7.34 (m, 8H), 2.49 (s, 3H), 2.37 (s, 3H) ppm.
MS (EI, m/z): 182 [M+]
(11)
Me
1-p-tolylnaphthalene (2h) 12
1H NMR (400 MHz, CDCl3, TMS): δ 7.92 (d, J = 8.0 Hz, 1H), 7.88 (d, J = 8.0 Hz,
1H), 7.82 (d, J = 8.0 Hz, 1H), 7.50 (m, 6H), 7.28 (d, J = 8.0 Hz, 2H), 2.43 (s, 3H)
ppm. MS (EI, m/z): 218 [M+]
S6
(12)

Cl
Me
(E)-1-chloro-4-(4-methylstyryl)benzene (2i) 13
1H NMR (400 MHz, CDCl3, TMS): δ 7.43 (m, 4H), 7.31 (d, J = 8.4 Hz, 2H), 7.17
(d, J = 7.6 Hz, 2H), 7.07 (2d, J = 9.6, 25.2 Hz, 2H), 2.36 (s, 3H) ppm. MS (EI,
m/z): 228 [M+]
(13)
Me
(E)-1-methyl-4-styrylbenzene (2j) 14
1H NMR (400 MHz, CDCl3, TMS): δ 7.50 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 8.0 Hz,
2H), 7.36 (t, J = 7.6 Hz, 2H), 7.25 (t, J = 7.6 Hz, 1H), 7.17 (d, J = 8.0 Hz, 2H),
7.07 (2d, J = 2.0, 18.0 Hz, 2H), 2.35 (s, 3H) ppm. MS (EI, m/z): 194 [M+]
(14)
(15)
(16)
CF3
4-(trifluoromethyl)biphenyl (2k) 15
1H NMR (400 MHz, CDCl3, TMS): δ 7.68 (s, 4H), 7.59 (d, J = 7.2 Hz, 2H), 7.48 (t,
J = 7.2 Hz, 2H), 7.41 (t, J = 7.2 Hz, 1H) ppm. MS (EI, m/z): 222 [M+]
OMe
4-methoxybiphenyl (2l) 16
1H NMR (400 MHz, CDCl3, TMS): δ 7.55 (m, 4H), 7.43 (m, 2H), 7.31 (m, 1H),
6.98 (d, J = 8.4 Hz, 2H), 3.85 (s, 3H) ppm. MS (EI, m/z): 184 [M+]
S7

Me
2-methylbiphenyl (2m) 11
1H NMR (400 MHz, CDCl3, TMS): δ 7.38 (m, 2H), 7.30 (m, 3H), 7.22(m, 4H),
2.25 (s, 3H) ppm. MS (EI, m/z): 168 [M+]
(17)
1-phenylnaphthalene (2n) 15
1H NMR (400 MHz, CDCl3, TMS): δ 7.90 (t, J = 5.2 Hz, 2H), 7.84 (d, J = 8.0 Hz,
1H), 7.52 (m, 6H), 7.42 (m, 3H) ppm. MS (EI, m/z): 204 [M+]
(18)
CN
biphenyl-2-carbonitrile (2o) 17
1H NMR (400 MHz, CDCl3, TMS): δ 7.76 (d, J = 7.6 Hz, 1H), 7.65 (t, J = 7.6 Hz,
1H), 7.56 (d, J = 7.2 Hz, 2H), 7.48 (m, 5H) ppm. MS (EI, m/z): 179 [M+]
(19)
Cl
(E)-1-chloro-4-styrylbenzene (2p) 18
1H NMR (400 MHz, CDCl3, TMS): δ 7.51 (d, J = 7.2 Hz, 2H), 7.45 (d, J = 8.4 Hz,
2H), 7.38 (m, 5H), 7.11 (2d, J = 3.2, 19.6 Hz, 2H) ppm. MS (EI, m/z): 214 [M+]
S8
(20)

(E)-1,2-diphenylethene (2q) 19
1H NMR (400 MHz, CDCl3, TMS): δ 7.52 (d, J = 7.6 Hz, 4H), 7.37 (m, 4H), 7.25
(m, 2H), 7.10 (s, 2H) ppm. MS (EI, m/z): 180 [M+]
(21)
CF3
Me
2-methyl-4'-(trifluoromethyl)biphenyl (2r) 20
1H NMR (400 MHz, CDCl3, TMS): δ 7.80 (m, 3H), 7.52 (m, 2H), 7.38 (m, 4H),
2.34 (m, 3H) ppm. MS (EI, m/z): 236 [M+]
(22)
Me
1-o-tolylnaphthalene (2s) 21
1H NMR (400 MHz, CDCl3, TMS): δ 7.89 (m, 2H), 7.54 (m, 3H), 7.34 (m, 6H), 2.03
(s, 3H) ppm. MS (EI, m/z): 218 [M+]
(23)
OMe
Me
4'-methoxy-2-methylbiphenyl (2t) 22
1H NMR (400 MHz, CDCl3, TMS): δ 7.25 (m, 6H), 6.95 (d, J = 8.0 Hz, 2H), 3.85 (s,
3H), 2.28 (s, 3H) ppm. MS (EI, m/z): 199 [M+]
S9
(24)

N
N
2-o-tolylpyrimidine (2u) 23
1H NMR (400 MHz, CDCl3, TMS): δ 8.86 (d, J = 5.2 Hz, 2H), 7.77 (d, J = 7.2 Hz,
1H), 7.35 (m, 3H), 7.24 (m, 1H), 2.52 (s, 3H) ppm. MS(EI, m/z): 170 [M+]
(25)
(26)
(27)
Me
Cl
(E)-1-(4-chlorostyryl)-2-methylbenzene (2v) 24
1H NMR (400 MHz, CDCl3, TMS): δ 7.57 (d, J = 6.4 Hz, 1H), 7.44 (d, J = 8.4 Hz,
2H), 7.32 (m, 5H), 7.10 (d, J = 7.2 Hz, 1H), 6.95 (d, J = 16.4 Hz, 1H), 2.41 (s, 3H)
ppm. MS (EI, m/z): 228 [M+]
Me
(E)-1-methyl-2-styrylbenzene (2w) 25
1H NMR (400 MHz, CDCl3, TMS): δ 7.58 (d, J = 6.8 Hz, 1H), 7.51 (d, J = 6.8 Hz,
2H), 7.36 (m, 2H), 7.24 (m, 5H), 7.00 (t, J = 16.4 Hz, 1H), 2.41 (s, 3H) ppm. MS
(EI, m/z): 194 [M+]
N
Me
Me
2,6-dip-tolylpyridine (2x) 26
S10
1H NMR (400 MHz, CDCl3, TMS): δ 8.05 (d, J = 8.0 Hz, 4H), 7.78 (t, J =8.4 Hz, 1H),

7.64 (d, J =8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 4H), 2.41 (s, 6H) ppm. MS (EI, m/z):
259 [M+]
(28)
Me
Me
1,3-di(4-methylphenyl)benzene (2y) 27
1H NMR (400 MHz, CDCl3, TMS): δ 7.77 (s, 1H), 7.55 (d, J = 8.0 Hz, 6H), 7.47 (m,
1H), 7.27 (d, J = 8.0 Hz, 4H), 2.40 (s, 6H) ppm. MS (EI, m/z): 258 [M+]
(29)
Me
Me
1,4-di(4-methylphenyl)benzene (2z) 28
1H NMR (400 MHz, CDCl3, TMS): δ 7.64 (s, 4H), 7.54 (d, J = 7.6 Hz, 4H), 7.27 (d,
J = 7.6 Hz, 4H), 2.40 (s, 6H) ppm. MS (EI, m/z): 258 [M+]
(30)
N
2,6-diphenylpyridine (2a’) 29
1H NMR (400 MHz, CDCl3, TMS): δ 8.16 (d, J = 8.0 Hz, 4H), 7.82 (t, J = 7.6 Hz,
1H), 7.69 (d, J = 8.0 Hz, 2H), 7.51 (t, J = 7.6 Hz, 4H), 7.44 (t, J = 7.4 Hz, 2H)
ppm. MS (EI, m/z): 231 [M+]
(31)
S11

1,3-diphenylbenzene (2b’) 30
1H NMR (400 MHz, CDCl3, TMS): δ 7.81 (s, 1H), 7.66 (d, J = 7.6 Hz, 4H), 7.58
(d, J = 7.6 Hz, 2H), 7.53 (d, J = 7.2 Hz, 1H), 7.45 (t, J = 7.6 Hz, 4H), 7.38 (t, J =
7.6 Hz, 2H) ppm. MS (EI, m/z): 230 [M+]
(32)
1,4-diphenylbenzene (2c’) 15
1H NMR (400 MHz, CDCl3, TMS): δ 7.67 (s, 8H), 7.47 (t, J = 8.0 Hz, 4H), 7.37 (d,
J = 8.0 Hz, 2H) ppm. MS (EI, m/z): 230 [M+]
ꢀ
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ꢀ
Spectra.
S13

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