Kumada-Tamao-Corriu Coupling of Heteroaromatic Chlorides and Aryl Ethers Catalyzed by [(IPr)Ni(allyl)Cl]

Kumada-Tamao-Corriu Coupling of Heteroaromatic Chlorides and Aryl Ethers Catalyzed by [(IPr)Ni(allyl)Cl] María José Iglesias, Auxiliadora Prieto,*, M. Carmen Nicasio*, Laboratorio de Catálisis Homogénea, Departamento de Química y Ciencias de los Materiales, Unidad Asociada al CSIC, Centro de Investigación en Química Sostenible (CIQSO), Campus de El Carmen s/n, Universidad de Huelva, 21007-Huelva, Spain. Departamento de Ingeniería Química, Química Física y Química Orgánica, Universidad de Huelva, 21007-Huelva, Spain and Departamento de Química Inorgánica, Universidad de Sevilla, Aptdo 1203, 41071-Sevilla, Spain. maria.prieto@diq.uhu.es; mnicasio@us.es Supporting Information Table of Contents General methods and experimental procedures 2-13 References 13-14 NMR spectra of compounds 15-53

General Methods. All reactions and manipulations were carried out under an oxygen-free nitrogen atmosphere with standard Schlenk techniques. All substrates were purchased from Aldrich and used as received. Solvents were dried and degassed before use. Imidazolium salts 1 and complexes 1-5 2 were prepared according to the literature procedures. NMR spectra were recorded on a Varian Mercury 400 MHz spectrometer. 1 H NMR shifts were measured relative to deuterated solvents peaks but are reported relative to tetramethylsilane. Elemental analyses were performed in Unidad de Análisis Elemental of the Universidad de Huelva. General Catalytic Procedure for kumada Reactions. The catalyst [(IPr)Ni(π-allyl)Cl] (0.05-0.001 mmol), Grignard reagent (1.5 mmol) and heteroaromatic chloride or arylmethyl ether (1 mmol) were added in turn to ampoule equipped with a magnetic bar under nitrogen atmosphere. The reaction was stirred at a given temperature for a given time (1-24h). The reaction was quenched through the addition of water and the mixture was extracted with CH 2 Cl 2 (3x5ml). The combined organic layers were dried over MgSO 4 and the solvent was evaporated in vacuo. The product was purified by column chromatography on silica gel to afford the desired product. Data of compounds shown in table 2: 2-Phenylpyridine 3 (Table 2, entry 1) Following the general procedure, the catalyst (0.001 mmol), the phenylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chloropyridine (1mmol) were stirred at room temperature for 1 h. The product was isolated as a colorless oil (152.6 mg, 86%) after purification (AcOEt/Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.20 (q, 1H, J = 4.8 Hz), 7.40-7.50 (m, 4H), 7.70 (d, 2H, J = 8.0 Hz), 8.00 (d, 2H, J = 8.0 Hz), 8.70 (d, 1H, J = 4.8 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 120.6, 122.1, 126.9, 128.8, 129.4, 136.8, 139.3, 149.6, 157.4. 2-p-Tolylpyridine 3 (Table 2, entry 2) Following the general procedure, the catalyst (0.001 mmol), the p-tolylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chloropyridine (1mmol) were stirred at room temperature for 1 h. The product was isolated as a colorless oil (171.4 mg, 99%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.40 (s, 3H), 7.16 (dd, 1H, J = 8.7, 4.6 Hz), 7.28 (d, 2H, J = 8.4 Hz), 7.67 (d, 2H, J = 4.9 Hz), 7.92 (d, 2H, J 2

= 8.0 Hz), 8.68 (d, 1H, J = 4.8 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.3, 120.3, 121.8, 126.8, 129.5, 136.6, 136.7, 138.9, 149.6, 157.4. 2-Mesitilpyridine 4 (Table 2, entry 3) Following the general procedure, the catalyst (0.001 mmol), the 2-mesitylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chloropyridine (1mmol) were stirred at room temperature for 5h. The product was isolated as a colorless oil (187.3 mg, 95%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.33 (s, 6H), 2.63 (s, 3H), 7.24 (s, 2H), 7.51-7.56 (m, 2H), 8.03 (t, 1H, J = 7.6 Hz), 9.01 (d, 1H, J = 4.9 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 20.1, 21.1, 121.5, 124.6, 128.2, 135.6, 136.2, 137.3, 137.7, 149.6, 160.1. 2-Phenylquinoline 5 (Table 2, entry 4) Following the general procedure, the catalyst (0.001 mmol), the phenylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chloroquinoline (1mmol) were stirred at room temperature for 2 h. The product was isolated as a white solid (203.9 mg, 99%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.37-7.41 (m, 1H), 7.44-7.47 (m, 3H), 7.66 (t, 1H, J = 7.7 Hz), 7.75 (d, 1H, J = 8.1 Hz), 7.80 (d, 1H, J = 8.6 Hz), 8.08-8.11 (m, 3H), 8.14 (d, 1H, J = 8.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 119.0, 126.2, 127.1, 127.4, 127.5, 128.8, 129.3, 129.6, 129.7, 136.8, 139.6, 148.2, 157.3. 2-(p-Tolyl)quinoline 6 (Table 2, entry 5) Following the general procedure, the catalyst (0.001 mmol), the p-tolylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chloroquinoline (1 mmol) were stirred at room temperature for 2h. The product was isolated as a white solid (207.1 mg, 94%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.36 (s, 3H), 7.26 (d, 2H, J = 8.0 Hz), 7.43 (t, 1H, J = 7.5 Hz), 7.64 (t, 1H, J = 7.7 Hz), 7.73 (d, 1H, J = 8.1 Hz), 7.78 (d, 1H, J = 8.6 Hz), 7.99 (d, 2H, J = 8.0 Hz), 8.10 (dd, 2H, J = 12.9, 8.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.3, 118.8, 126.0, 127.0, 127.4, 129.5, 129.6, 136.6, 136.8, 139.3, 148.2, 157.4. 3

N, N-Dimethyl-4-(quinolin-2-yl)aniline 7 (Table 2, entry 6) Following the general procedure, the catalyst (0.001 mmol), the 4-(N,Ndimethyl)anilinemagnesium bromide (0.5M in THF) (1.5 mmol) and 2-chloroquinoline (1 mmol) were stirred at room temperature for 1h. The product was isolated as a yellow solid (226.1 mg, 95%) after purification (AcOEt/ Petroleum Ether 1:40) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.97 (s, 6H), 6.76 (d, 2H, J = 8.0 Hz), 7.38 (t, 1H, J = 8.0 Hz), 7.60 (d, 1H, J = 8.0 Hz), 7.69 (d, 1H, J = 8.0 Hz) 7.75 (d, 1H, J = 8.0 Hz), 8.02-8.06 (m, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 40.3, 112.2, 118.3, 125.3, 126.6, 127.3, 128.4, 129.2, 136.3, 148.3, 151.3, 157.3. 3-Mesitylquinoline 8 (Table 2, entry 7) Following the general procedure, the catalyst (0.001 mmol), the 2-mesitylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chloroquinoline (1 mmol) were stirred at room temperature for 2h. The product was isolated as a colorless oil (224.1 mg, 99%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.34 (s, 6H), 2.61 (s, 3H), 7.24 (s, 2H), 7.61 (d, 1H, J = 8.3 Hz), 7.81 (t, 1H, J = 7.5 Hz), 7.99 (t, 1H, J = 7.6 Hz), 8.11 (d, 1H, J = 8.2 Hz), 8.46 (t, 2H, J = 9.1 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 20.2, 21.2, 122.9, 126.4, 126.7, 127.6, 128.5, 128.9, 129.5, 135.6, 136.3, 137.6, 137.9, 148.2, 160.7. 3-Phenylpyridine 3 (Table 2, entry 8) Following the general procedure, the catalyst (0.01 mmol), the phenylmagnesium bromide (1M in THF) (1.5 mmol) and 3-chloropyridine (1mmol) were stirred at room temperature for 8 h. The product was isolated as a colorless oil (137.6 mg, 89%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.16-7.20 (m, 1H), 7.25 (t, 1H, J = 7.2 Hz), 7.32 (t, 2H, J = 7.2 Hz), 7.42 (d, 2H, J = 7.9 Hz), 7.69 (d, 1H, J = 8.0 Hz), 8.45 (d, 1H, J = 4.8 Hz), 8.72 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 123.5, 127.0, 128.0, 129.0, 134.2,136.5, 137.7, 148.2, 148.4. 4

3-p-Tolylpyridine 9 (Table 2, entry 9) Following the general procedure, the catalyst (0.01 mmol), the p-tolylmagnesium bromide (1M in THF) (1.5 mmol) and 3-chloropyridine (1mmol) were stirred at room temperature for 8 h. The product was isolated as a colorless oil (157.2 mg, 93%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.23 (s, 3H), 7.10 (d, 2H, J = 7.9 Hz), 7.14 (dd, 1H, J =7.9, 4.8 Hz), 7.30 (d, 2H, J = 7.8 Hz), 7.65 (d, 1H, J = 7.9 Hz), 8.41 (d, 1H, J = 4.4 Hz), 8.69 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 21.1, 123.4, 126.8, 129.7, 134.0, 134.8, 136.4, 137.9, 148.0, 148.1. 3-Mesitylpiridine 10 (Table 2, entry 10) Following the general procedure, the catalyst (0.01 mmol), the 2-mesitylmagnesium bromide (1M in THF) (0.75 mmol) and 3-chloropyridine (0.5 mmol) were stirred at room temperature for 8h. The product was isolated as a colorless oil (57.5 mg, 29%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.91 (s, 6H), 2.25 (s, 3H), 6.88 (s, 2H), 7.25-7.28 (m, 1H), 7.41 (d, 1H, J = 7.6 Hz), 8.34 (s, 1H), 8.50 (d, 1H, J = 4.8 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 20.8, 21.0, 123.3, 128.3, 134.9, 136.21, 136.6, 137.0, 137.5, 148.0, 150.2. 2-(p-Tolyl)thiophene 11 (Table 2, entry 11) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chlorothiophene (0.5 mmol) were stirred at room temperature for 12h. The product was isolated as a white solid (85.3 mg, 98%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.26 (s, 3H), 6.96 (dd, 1H, J = 5.1, 3.6 Hz), 7.08 (d, 2H, J = 8.4 Hz) 7.14 (dd, 1H, J = 5.1, 1.2 Hz), 7.17 (dd, 1H, J = 3.6, 1.2 Hz), 7.41 (d, 2H, J = 8.2 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.2, 122.6, 124.3, 125.9, 128.0, 129.6, 131.7, 137.5, 144.6. 2-Mesitylthiophene 12 (Table 2, entry 12) Following the general procedure, the catalyst (0.05 mmol), the mesitylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chlorothiophene (0.5 mmol) were stirred at room temperature for 12h. The product was isolated as a white solid (100 mg, 99%) after purification (Petroleum 5

Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.12 (s, 6H), 2.32 (s, 3H), 6.80-6.81 (m, 1H), 6.94 (br s, 2H) 7.09-7.11 (m, 1H), 7.35-7.37 (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 15.5, 15.9,120.0, 121.2, 121.8, 122.9, 125.8, 132.6, 133.1, 136.2. 2-Phenylpyrimidine 13 (Table 2, entry 13) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chloropyrimidine (0.5 mmol) were stirred at room temperature for 24h. The product was isolated as a colorless oil (64.7 mg, 72%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.19 (t, 1H, J = 4.8 Hz), 7.49-7.51 (m, 3H), 8.43-8.46 (m, 2H), 8.81 (d, 2H, J = 4.8 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 119.1, 128.1, 128.6, 130.7, 130.7, 137.5, 157.5, 164.7. p-tolylpyrimidine 9 (Table 2, entry14) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chloropyrimidine (0.5 mmol) were stirred at room temperature for 24h. The product was isolated as a colorless oil (76.4 mg, 74%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.34 (s, 3H), 7.06 (t, 1H, J = 4.8 Hz), 7.22 (d, 2H, J = 8.0 Hz), 8.25 (d, 2H, J = 8.1 Hz), 8.70 (d, 2H, J = 4.9 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.4, 118.7, 128.0, 129.3, 134.8, 141.0, 157.1, 164.8. 1-Methyl-2-(p-tolyl)imidazole 14 (Table 2, entry 15) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 1-methyl-2-chloroimidazole (0.5 mmol) were stirred at room temperature for 12h. The product was isolated as a yellow solid (41.3 mg, 48%) after purification (AcOEt) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.23 (s, 3H), 3.66 (s, 3H), 6.88 (d, 1H, J = 1.1 Hz), 7.03 (d, 1H, J = 1.1 Hz), 7.18-7.20 (m, 2H), 7.45 (d, 2H, J = 8.2 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.3, 34.5, 122.1, 125.7, 127.7, 128.3, 128.5, 129.0, 129.2, 138.5, 148.0. 6

2-Phenylthiazole 15 (Table 2, entry 16) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chlorothiazole (0.5 mmol) were stirred at room temperature for 12h. The product was isolated as a yellow solid (74.9 mg, 93%) after purification (Et 2 O/Petroleum Ether 1:5) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.25 (d, 1H, J = 3.3 Hz), 7.34-7.38 (m, 3H), 7.79 (d, 1H, J = 3.3 Hz), 7.88-7.90 (m, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 118.9, 126.6, 129.0, 130.0, 133.5, 143.7, 168.4. 2-(p-tolyl)thiazole 16 (Table 2, entry 17) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chlorothiazole (0.5 mmol) were stirred at room temperature for 12h. The product was isolated as a yellow solid (83.1 mg, 95%) after purification (Et 2 O/Petroleum Ether 1:5) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.31 (s, 3H), 7.17 (d, 2H, J = 8.7 Hz), 7.21 (d, 1H, J = 3.3 Hz), 7.76 (d, 1H, J = 3.3 Hz), 7.78 (d, 2H, J = 8.3 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.4, 118.4, 126.5, 129.7, 130.9, 140.2, 143.5, 168.6. N O 2-Mesitylbenzoxazole 17 (Table 2, entry 18) Following the general procedure, the catalyst (0.02 mmol), the 2-mesitylmagnesium bromide (1M in THF) (1.5 mmol) and 2-chlorobenzoxazole (1 mmol) were stirred at room temperature for 24h. The product was isolated as a colorless oil (227.1 mg, 96%) after purification (AcOEt/ Petroleum Ether 1:40) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.35 (s, 6H), 2.38 (s, 3H), 7.01 (s, 2H), 7.39-7.43 (m, 2H), 7.61-7.63 (m, 1H), 7.88-7.90 (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 20.4, 21.3, 110.6, 120.1, 124.3, 124.9, 125.0, 128.7, 129.0, 138.5, 140.3, 141.6, 150.6, 163.3. 2-Phenylbenzotiazole 3 (Table 2, entry 19) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chlorobenzothiazole (0.5 mmol) were stirred at room temperature for 24h. The product was isolated as a yellow solid (77.9 mg, 74%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.28 (t, 1H, J = 7.6 Hz), 7.38-7.40 (m, 4H), 7.79 (d, 1H, J = 8.6 Hz), 7.98-8.01 (m, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 121.6, 123.2, 125.2, 126.3, 127.5, 129.0, 130.9, 133.5, 135.0, 154.1, 168.0. 7

2-(p-Tolyl)benzotiazole 6 (Table 2, entry 20) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chlorobenzothiazole (0.5 mmol) were stirred at room temperature for 24h. The product was isolated as a yellow solid (113.6 mg, 88%) after purification (AcOEt/ Petroleum Ether 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.27 (s, 3H), 7.14 (d, 2H, J = 8.4 Hz), 7.22 (t, 1H, J = 8.1 Hz) 7.34 (t, 1H, J = 8.0 Hz), 7.73 (d, 1H, J = 8.0 Hz), 7.85 (d, 2H, J = 8.2 Hz), 7.94 (d, 1H, J = 8.2 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.5, 121.5, 123.0, 124.9, 126.2, 127.4, 129.7, 130.9, 134.9, 141.3, 154.2, 168.1. Data of compounds shown in table 3: 2-Phenylnaphtalene 18 (Table 3, entry 1) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chloronaphthalene (0.5 mmol) were stirred at room temperature for 24h. The product was isolated as a white solid (84.7 mg, 82%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.46 (t, 1H, J = 6.7 Hz), 7.54-7.58 (m, 4H), 7.79-7.84 (m, 3H), 7.93-7.99 (m, 3H), 8.12 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 125.6, 125.8, 125.9, 126.3, 127.4, 127.4, 127.7, 128.2, 128.4, 128.9, 132.6, 133.7, 138.5, 141.1. 2-(p-Tolyl)naphthalene 18 (Table 3, entry 2) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 2-chloronaphthalene (0.5 mmol) were stirred at room temperature for 24h. The product was isolated as a white solid (84.6 mg, 94%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.27 (s, 3H), 7.12 (d, 2H, J = 7.7 Hz), 7.29-7.32 (m, 2H), 7.46 (d, 2H, J = 7.8 Hz), 7.58 (d, 1H, J = 8.5 Hz), 7.67-7.73 (m, 3H), 7.87 (s, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 21.2, 125.5, 125.6, 125.8, 126.3, 127.3, 127.7, 128.2, 128.4, 129.6, 132.6, 133.8, 137.2, 138.3, 138.5. 8

4-Methylbiphenyl 19 (Table 3, entry 3) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 4-methylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a colorless oil (82.1 mg, 95%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.26 (s. 3H), 7.12 (d, 2H, J = 8.2 Hz), 7.20 (t, 1H, J = 7.2 Hz), 7.29 (t, 2H, J = 7.6 Hz), 7.37 (d, 2H, J = 8.1 Hz), 7.46 (d, 2H, J = 7.1 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.2, 127.0, 128.8, 129.5, 137.1, 138.4, 141.2. 4,4 -Dimethylbiphenyl 3 (Table 3, entry 4) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 4-methylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (71.5 mg, 95%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.53 (s, 6H), 7.37 (d, 4H, J = 8.4 Hz), 7.63 (d, 4H, J = 8.1 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.2, 126.9, 129.6, 136.8, 138.4. 4-(N,N -Dimethylamino)-4 -metylbiphenyl 20 (Table 3,entry 5) Following the general procedure, the catalyst (0.05 mmol), the 4-(N,Ndimethyl)anilinemagnesium bromide (0.5M in THF) (0.75 mmol) and 4-methylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (84.8 mg, 95%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.47 (s, 3H), 3.06 (s, 6H), 6.88 (d, 2H, J = 8.4 Hz), 7.30 (d, 2H, J = 7.9 Hz), 7.56 (d, 2H, J = 8.5 Hz), 7.59 (d, 2H, J = 8.5 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.1, 40.7, 112.8, 126.2, 127.5, 129.3, 129.4, 135.6, 138.4, 149.8. 4-Ethyl-biphenyl 21 (Table 3, entry 6) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and ethylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a colorless oil (80.1 mg, 88%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.42 (t, 3H, J = 7.6 Hz), 2.83 (q, 2H, J = 8.1 Hz), 7.40-7.49 (m, 3H), 7.56 (q, 2H, J = 7.6 Hz), 7.66 (d, 2H, J = 8.1 Hz), 7.73 (d, 2H, J = 7.2 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 15.7, 28.6, 127.0, 127.1, 127.2, 128.4, 128.8, 138.7, 141.2, 143.4. 9

4-Ethyl-4 -methylbiphenyl 9 (Table 3, entry 7) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and ethylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (87.6 mg, 88%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.16 (t, 2H, J = 7.6 Hz), 2.27 (s, 3H), 2.57 (q, 2H, J = 7.6 Hz), 7.12 (d, 2H, J = 8.0 Hz), 7.15 (d, 2H, J = 8.0 Hz), 7.36-7.41 (m, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 15.6, 21.1, 28.5, 126.9, 127.0, 128.3, 129.4, 136.7, 138.3, 138.6, 143.1. 4-Ethyl-4 -(N,N-dimethylamino)biphenyl (Table 3, entry 8) Following the general procedure, the catalyst (0.05 mmol), the 4-(N,Ndimethyl)anilinemagnesium bromide (0.5M in THF) (0.75 mmol) and ethylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a colorless oil (85.6 mg, 80%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.18 (t, 3H, J = 7.6 Hz), 2.58 (q, 2H, J = 7.6 Hz), 2.88 (s, 6H), 6.71 (d, 2H, J = 8.2 Hz), 7.15 (d, 2H, J = 8.4 Hz), 7.39-7.42 (m, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 15.7. 28.5, 40.6, 112.8, 126.2, 127.6, 128.2, 129.3, 138.6, 142.0, 149.8. Anal. Calcd. for: C 16 H 19 N: C, 85.28, H, 8.50 N, 6.22. Found C, 85.09, H, 8.51, N, 6.19. 4-tert-Butylbiphenyl 22 (Table 3, entry 9) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 4-tert-butylanisole (0.5 mmol) were stirred at 80ºC for 12h. The product was isolated as a colorless oil (59.6 mg, 59%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.43 (s, 9H), 7.39 (q, 1H, J = 8.3 Hz), 7.45-7.54 (m, 4H), 7.60 (d, 2H, J = 8.3 Hz), 7.65 (d, 2H, J = 8.0 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 31.4, 34.5, 125.7, 126.8, 127.0, 127.1, 127.2, 127.3, 128.7, 128.8, 138.3, 141.0, 141.2, 150.2. 4-Methyl-4 -tert-butylbiphenyl 22 (Table 3, entry 10) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 4-tert-butylanisole (0.5 mmol) were stirred at 80ºC for 12h. The product was isolated as a white solid (75.4 mg, 67%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.26 (s, 9H), 2.29 (s, 3H), 7.13 (d, 2H, J = 10

8.4 Hz), 7.34-7.44 (m, 6H). 13 C NMR (100 MHz, CDCl 3 ) δ 21.1, 31.4, 34.5, 125.7, 126.6, 126.8, 126.9, 129.4, 136.7, 138.1, 138.2, 149.9. 4-tert-Butyl-4 -(N,N -dimethylamino)biphenyl 23 (Table 3, entry 11) Following the general procedure, the catalyst (0.05 mmol), the 4-(N,Ndimethyl)anilinemagnesium bromide (0.5M in THF) (0.75 mmol) and 4- tert-butylanisole (0.5 mmol) were stirred at 80ºC for 12h. The product was isolated as a white solid (66.9 mg, 52%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 1.37 (s, 9H), 3.00 (s, 6H), 6.82 (d, 2H, J = 8.6 Hz), 7.44 (d, 2H, J = 8.3 Hz), 7.52 (d, 4H, J = 8.6 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 31.4, 34.4, 40.6, 112.8, 125.5, 125.9, 127.6, 129.2, 138.3, 148.8, 149.7. PhH 2 C 4-Benzyl-4 -methylbiphenyl 24 (Table 3, entry 12) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 4-benthylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (109.7 mg, 85%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.29 (s, 3H), 3.92 (s, 2H), 7.11-7.16 (m, 7H), 7.19-7.23 (m, 2H), 7.38 (d, 2H, J = 8.1 Hz), 7.41 (d, 2H, J = 8.2 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.2, 41.6, 126.2, 126.9, 127.1, 128.6, 129.0, 129.3, 129.5, 136.9, 138.1, 139.0, 139.9, 141.1. 3-Methylbiphenyl 25 (Table 3, entry 13) Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 3-methylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a colorless oil (63.1 mg, 75%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.47 (s, 3H), 7.21 (d, 1H, J = 7.4 Hz), 7.39 (q, 2H, J = 8.0 Hz), 7.44-7.51 (m, 4H), 7.63-7.66 (m, 2H,). 13 C NMR (100 MHz, CDCl 3 ) δ 21.6, 124.3, 127.2, 127.3, 128.0, 128.1, 128.7, 128.8, 138.3, 141.2, 141.3. 3,4 -Dimethylbiphenyl 26 (Table 3, entry 14) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 3-methylanisole (0.5 mmol) were stirred at 60ºC for 12h. The product 11

was isolated as a colorless oil (74.7 mg, 81%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.30 (s, 3H), 2.32 (s, 3H), 7.05 (d, 1H, J = 7.1 Hz), 7.14 (d, 2H, J = 8.4 Hz), 7.22 (t, 1H, J = 7.5 Hz), 7.28 (d, 2H, J = 8.6 Hz), 7.38 (d, 2H, J = 8.1 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.1, 21.6, 124.1, 127.0, 127.7, 127.8, 128.6, 129.4, 136.9, 138.3, 138.4, 141.1. 4'-Methyl-4-trifluoromethyl-biphenyl 27 (Table 3, entry 15) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and 4-(trifluoromethyl)anisole (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (66.1 mg, 58%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.40 (s, 3H), 7.27 (d, 2H, J = 7.8 Hz), 7.48 (d, 2H, J = 8.1 Hz), 7.66 (s, 4H). 13 C NMR (100 MHz, CDCl 3 ) δ 21.1,125.6, 127.1, 129.7, 136.8, 138.1, 144.6. N-Benzyl-(4-tolyl)aniline (Table 3, entry 16) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (0.75 mmol) and N-benzyl-4-methoxyaniline (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (66.9 mg, 49%) after purification (Et 2 O/Petroleum Ether 1:25) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.39 (s, 3H), 4.14 (br s, 1H), 4.39 (s, 2H), 6.72 (d, 2H, J = 8.6 Hz), 7.23 (d, 2H, J = 8.0 Hz), 7.31-7.36 (m, 1H), 7.36-7.47 (m, 8H). 13 C NMR (100 MHz, CDCl 3 ) δ 21.1, 48.4, 113.1, 127.3, 127.5, 127.8, 128.7, 128.7, 129.4, 130.5, 135.7, 138.4, 139.3, 147.3. 1,4-Diphenylbenzene 28 (Table 3, entry 17) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (1.0 mmol) and 1,4-dimethoxybenzene (0.5 mmol) were stirred at 60ºC for 12h. The product was isolated as a white solid (102.4 mg, 89%) after purification (Petroleum Ether) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.29 (t, 2H, J = 7.2 Hz), 7.39 (t, 4H, J = 7.5 Hz), 7.58 (d, 4H, J = 7.5 Hz), 7.61 (s, 4H). 13 C NMR (100 MHz, acetone-d 6 ) δ 127.1, 127.4, 127.5, 128.8, 140.1, 140.7. 2-Phenylpyridine 3 (Table 3, entry 18) 12

Following the general procedure, the catalyst (0.05 mmol), the phenylmagnesium bromide (1M in THF) (0.75 mmol) and 2-methoxypyridine (0.5mmol) were stirred at 60ºC for 24 h. The product was isolated as a colorless oil (55.3 mg, 71%) after purification (AcOEt/PE 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 7.20 (q, 1H, J = 4.8 Hz), 7.40-7.50 (m, 4H), 7.70 (d, 2H, J = 8.0 Hz), 8.00 (d, 2H, J = 8.0 Hz), 8.70 (d, 1H, J = 4.8 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 120.6, 122.1, 126.9, 128.8, 129.4, 136.8, 139.3, 149.6, 157.4. 2-p-Tolylpyridine 3 (Table 3, entry 19) Following the general procedure, the catalyst (0.05 mmol), the p-tolylmagnesium bromide (1M in THF) (1.5 mmol) and 2-methoxypyridine (0.5mmol) were stirred at 60ºC for 24 h. The product was isolated as a colorless oil (79.4 mg, 95%) after purification (AcOEt/PE 1:20) by flash chromatography. 1 H NMR (400 MHz, CDCl 3 ) δ 2.40 (s, 3H), 7.16 (dd, 1H, J = 8.7, 4.6 Hz), 7.28 (d, 2H, J = 8.4 Hz), 7.67 (d, 2H, J = 4.9 Hz), 7.92 (d, 2H, J = 8.0 Hz), 8.68 (d, 1H, J = 4.8 Hz). 13 C NMR (100 MHz, CDCl 3 ) δ 21.3, 120.3, 121.8, 126.8, 129.5, 136.6, 136.7, 138.9, 149.6, 157.4. References 1. a) Arduengo, A. J. III; Kcafcyk, R.; Schuntzler R. Tetrahedron 1999, 55, 14523. b) Jafarpour, L.; Stevens, E. D.; Nolan, S. P. J. Org. Chem. 2000, 606, 49. 2. a) Dible, B. R.; Sigman, M. S. J. Am. Chem. Soc. 2003, 125, 872. b) Dible, B. R.; Sigman, M. S. Inorg. Chem. 2006, 45, 8430. 3. Dong-Hwan, L.; Minkee, C.; Byung-Woo, Y.; Ryong, R.; Abu, T.; Shahin, H.; Myung-Jong, J. Adv. Synth. Catal. 2009, 351, 2912. 4. Malmberg, H.; Nilsson, M. Tetrahedron 1986, 42, 3981. 5. Korivi, R. P.; Cheng, C.-H. J. Org. Chem. 2006, 71, 7079. 6. Egi, M.; Liebeskind, L. S. Org. Lett. 2003, 5, 801. 7. Tobisu, M.; Hyodo, I.; Chatani, N. J. Am. Chem. Soc. 2009, 131, 12070. 8. Hatakeyama, T.; Kakamura, M. J. Am. Chem. Soc. 2007, 129, 9844. 9. Iwasawa, T.; Ajami, D.; Rebek, J. Org. Lett. 2006, 8, 2925. 10. Barder, E. T.; Walker, S. D.; Martinelli, J. R.; Buchwald, S. L. J. Am. Chem. Soc. 2005, 127, 4685. 11. Tsai, F.-Y.; Lin, B.-N.; Chen, M.-J.; Moub, C.-Y.; Liub, S.-T. Tetrahedron 2007, 63, 4304. 12. Organ, M. G.; Abdel-Hadi, M.; Avola, S.; Hadei, N.; Nasielski, J.; O Brien, C. J.; Valente, C. Chem. Eur. J. 2007, 13, 150. 13. Anderson, E. D.; Boger, D. L. J. Am. Chem. Soc. 2011, 133, 12285. 13

14. Smolii, O. B.; Brovarets, V. S.; Pirozhenko, V. V.; Drach, B. S. Zhurnal Obshchei Khimii 1988, 58, 2635. 15. Noyce, D. S.; Fike, S. A. J. Org. Chem. 1973, 38, 2433. 16. Jensen, J.; Skjaerbaek, N.; Vedso, P. Synthesis 2001, 128. 17. Do, H.-Q.; Dauglis, O. J. Am. Chem. Soc. 2007, 129, 12404. 18. Li, B.-J.; Li, Y.-Z.; Lu, X.-Y.; Liu, J.; Guan, B.-T.; Shi, Z.-J. Angew. Chem. Int. Ed. 2008, 47, 10124. 19. Yoshikai, N.; Mashima, H.; Nakamura, E. J. Am. Chem. Soc. 2005, 127, 17978. 20. Inada, K.; Miyaura, N. Tetrahedron 2000, 56, 8657. 21. Karimi, B.; Elhamifar, D.; Clark, J.-H.; Hunt, A.-J. Chem. Eur. J. 2010, 16, 8047. 22. Cho, C.-H.; Yun, H.-S.; Park, K. J. Org. Chem. 2003, 68, 3017. 23 Boehmer, M. C.; Frye, E. C.; O Connell, M. G. K.; Galloway, W. R. J. D.; Sore, A. F.; Dominguez, P. G.; Norton, D.; Hulcoop, D. G.; Owen, M.; Turner, G.; Crawford, C.; Horsley, H.; Spring, D. R. Chem. Eur. J. 2011, 17, 13230. 24. Zhang, L.; Wu, J. Adv. Synth. Cat. 2008, 350, 2409. 25. Sawoo, S.; Srimani, D.; Dutta, P.; Lahiri, R.; Sarkar, A. Tetrahedron 2009, 65, 4367. 26. Zhang, L.; Wu, J. Adv. Synth. Catal. 2008, 350, 2409. 27. Liu, L.; Zhang, Y.; Xin, B. J. Org. Chem. 2006, 71, 3994. 28. Smith, G. W. J. Mol. Spectrosc.1964, 12, 146. 14

(Table 2, entry 1) 15

(Table 2, entry 3) N N 17

18 (Table 2, entry 4) 0.92 2.80 0.95 0.91 0.97 2.72 1.00 7.37 7.39 7.41 7.44 7.45 7.46 7.47 7.64 7.65 7.68 7.74 7.76 7.79 7.81 8.08 8.10 8.11 8.13 8.15 119.05 126.29 127.47 127.57 128.86 129.32 129.67 129.72 136.80 139.68 148.26 157.38 126.29 127.17 127.47 127.57 128.86 129.32 129.67 129.72

29 (Table 2, entry 15) 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 1.45 1.38 0.47 0.47 1.41 1.00 2.33 3.66 6.88 6.88 7.03 7.03 7.18 7.18 7.19 7.20 7.20 7.20 7.44 7.46 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 21.33 34.46 76.71 77.03 77.23 77.34 122.11 125.74 127.72 128.26 128.51 129.03 129.18 138.53 147.95

30 (Table 2, entry 16) 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 0.48 1.62 0.47 1.00 7.18 7.24 7.25 7.34 7.34 7.35 7.35 7.35 7.36 7.36 7.36 7.37 7.37 7.37 7.38 7.78 7.79 7.88 7.88 7.89 7.89 7.89 7.90 7.90 7.90 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 76.73 77.05 77.36 118.85 126.57 128.97 130.01 133.54 143.66 162.31 168.44

31 (Table 2, entry 17) 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 3.49 2.50 1.00 3.06 2.31 7.16 7.18 7.20 7.21 7.75 7.76 7.77 7.79 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 21.42 76.73 77.04 77.36 118.35 126.48 129.64 130.92 140.23 143.48 149.64 150.41 168.61

(Table 2, entry 18) 141.62 140.30 138.50 129.00 128.72 125.03 124.97 124.31 120.19 110.65 21.33 20.43 1.00 1.03 2.16 2.12 3.72 6.44 7.90 7.89 7.88 7.63 7.63 7.62 7.61 7.43 7.42 7.40 7.39 7.38 7.01 2.38 2.35 N O 163.35 150.66 N O 32

(Table 2, entry 19) N S 135 130 125 120 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0-10 33

(Table 3, entry 3) 230 220 210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0-10 37

(Table 3, entry 9) 1.00 0.57 1.57 0.53 2.49 7.67 7.64 7.62 7.59 7.54 7.52 7.50 7.48 7.46 7.42 7.40 7.38 7.36 1.43 Bu t Bu t 43

(Table 3, entry 10) Bu t Bu t 44

(Table 3, entry 11) Bu t N Bu t N 45

(Table 3, entry 15) CF 3 CF 3 49

50 (Table 3, entry 16) 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 1.52 0.47 1.04 1.00 0.99 0.57 4.02 2.39 4.14 4.39 6.71 6.71 6.73 6.73 7.22 7.23 7.26 7.38 7.40 7.41 7.41 7.43 7.43 7.45 7.45 7.46 7.46 7.47 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 21.07 48.35 76.74 77.06 77.38 113.09 126.18 127.29 127.50 127.78 128.69 129.38 130.47 135.72 138.37 139.34 147.33

51 (Table 3, entry 17) 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 0.47 1.00 2.01 7.19 7.28 7.29 7.31 7.38 7.39 7.41 7.57 7.59 7.61 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 115 120 125 130 135 140 145 150 76.73 77.05 77.36 127.07 127.36 127.52 128.84 140.12 140.69