Room-Temperature Kumada Cross-Coupling of Unactivated Aryl

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 [email protected]

Supporting Information

List of Contents

Figure S1, molecular structure and synthesis of 4 General remarks.

S2-S3 S3

General experimental procedure

S3

Characterization data the products in the coupling reaction.

S3-S12

References.

S12-S13

Spectra.

S14-S48

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’-ethoxyethyldiimidazolium 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: C, 35.76; H, 3.64; N, 11.30. 1H 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

Hz, 2H), 3.97 (t, J = 12.4 Hz, 4H), 3.61 (m, 2H), 3.48 (m, 2H) ppm. 13C 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)3,3’-ethoxyethyldiimidazolium dihexafluorophosphate1, Ni(PPh3)2Cl22, NHC nickel complexes 13, 24 and 33 were prepared according to the known procedure. Chemical shifts ( ) are expressed in ppm downfield to TMS at = 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 1

H NMR (400 MHz, CDCl3, TMS):

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 1

H NMR (400 MHz, CDCl3, TMS): 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 1


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 1


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) 1


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.

13

C NMR (100 MHz, CDCl3, TMS):

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) F3 C

Me

4-methyl-4'-(trifluoromethyl)biphenyl (2c) 9 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1


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 1


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 1


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) CF3

4-(trifluoromethyl)biphenyl (2k) 15 1

H NMR (400 MHz, CDCl3, TMS): 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+]

(15) OMe

4-methoxybiphenyl (2l) 16 1


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 (16)

Me

2-methylbiphenyl (2m) 11 1


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 1

H NMR (400 MHz, CDCl3, TMS): 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 1


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 1


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 1


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 1


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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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)

Me

Cl

(E)-1-(4-chlorostyryl)-2-methylbenzene (2v) 24 1

H NMR (400 MHz, CDCl3, TMS): 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+]

(26)

Me

(E)-1-methyl-2-styrylbenzene (2w) 25 1

H NMR (400 MHz, CDCl3, TMS): 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+]

(27)

N

Me

Me

2,6-dip-tolylpyridine (2x) 26 S10 1


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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1

H NMR (400 MHz, CDCl3, TMS): 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 1


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 1

H NMR (400 MHz, CDCl3, TMS): 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+]

References (1) Liu, B.; Chen, W.; Jin, S. Organometallics. 2007, 26, 3660. (2) Venanzi, L. M. J. Chem. Soc. 1958, 719. (3) Xi, Z.; Zhang, X.; Chen, W.; Fu, S.; Wang, D. Organometallics. 2007, 26, 6636. (4) Chiu, P. L.; Lai, C.-L.; Chang, C.-F.; Hu, C.-H.; Lee, H. M.

Organometallics

2005, 24, 6169. (5) Leadbeater, N. E.; Resouly, S. M. Tetrahedron 1999, 55, 11889. (6) Meek, J. S.; Merrow, R. T.; Cristol, S. J. J. Am. Chem. Soc. 1952, 74, 2667. (7) Tinnemans, A. H. A.; Laarhoven,W. H. J. Am. Chem. Soc. 1974, 96, 4611. (8) Burdeska, K.; Guglielmu, K.; Weber, K. Eur. Pat. Appl. 1981, 94. (9) Ackermann, L.; Althammer, A. Org. Lett. 2006, 8, 3457. (10) Dai, Q.; Gao, W.; Liu, D.; Kapes, L. M.; Zhang, X. J. Org. Chem. 2006, 71, 3928. (11) Guo, M.; Jian, F.; He, R. Tetrahedron Lett. 2006, 47, 2033. (12) Kingston, J. V.; Verkade, J. G. J. Org. Chem. 2007, 72, 2816. S12

(13) Wang, C.; Yan, L.; Zheng, Z.; Yang, D.; Pan, Y. Tetrahedron 2006, 66, 7712. (14) Lawrence, N. J.; Muhammad, F. Tetrahedron 1998, 54, 15361. (15) Shi, S.; Zhang, Y. J. Org. Chem. 2007, 72, 5927. (16) Shi, M.; Qian, H.-X. Tetrahedron 2005, 61, 4949. (17) Thimmaiah, M.; Fang, S. Tetrahedron 2007, 63, 6879. (18) Iranpoor, N.; Firouzabadi, H.; Azadi, R. Eur. J. Org. Chem. 2007, 13, 2197. (19) Alacid, E.; Najera, C. Adv. Synth. Catal. 2006, 348, 945. (20) Yamada, Y. M. A.; Maeda, Y.; Uozumi, Y. Org. Lett. 2006, 8, 4259. (21) Navarro, O.; Marion, N.; Oonishi, Y.; Kelly, R. A., III; Nolan, S. P. J. Org. Chem. 2006, 71, 685. (22) Li, J-H.; Zhu, Q-M.; Xie, Y-X. Tetrahedron 2006, 62, 10888. (23) Milne, J. E.; Buchwald, S. L. J. Am. Chem. Soc. 2004, 126, 13028. (24) Inoue, A.; Shinokubo, H.; Oshima, K. J. Am. Chem. Soc. 2003, 125, 1484. (25) Yao, Q.; Zabawa, M.; Woo, J.; Zheng, C. J. Am. Chem. Soc. 2007, 129, 3088. (26) Xi, Z.; Sato, K.; Gao, Y.; Lu, J.; Takahashi, T. J. Am. Chem. Soc. 2003, 125, 9568. (27) Limmert, M. E.; Roy, A. H.; Hartwig, J. F. J. Org. Chem. 2005, 70, 9364. (28) Dong, C-G.; Hu, Q-S. J. Am. Chem. Soc. 2005, 127, 10006. (29) Mousset, D.; Gillaizeau, I.; Sabatie, A.; Bouyssou, P.; Coudert, G. J. Org. Chem. 2007, 71, 5993. (30) Li, J.-H.; Li, J.-L.; Wang, D.-P.; Pi, S.-F.; Xie, Y.-X.; Zhang, M.-B.; Hu, X.-C. J. Org. Chem. 2007, 72, 2053. (31) Masami, K.; Rumiko, S.; Ryuichi, S. Tetrahedron 2007, 63, 9393.

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Room-Temperature Kumada Cross-Coupling of Unactivated Aryl

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