Supporting Information for. Table of Contents

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1 Supporting Information for Mengdi Zhao and Wenjun Lu* Department of Chemistry, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai , People s Republic of China Table of Contents 1. General General Procedure for Bromination Optimization for bromination of some substrates Data References Copies of 1 H NMR, 13 C NMR and DEPT-135 spectra for all products and some reaction mixture S1

2 1. General All reagents were commercially available, weighed out under ambient conditions and used without further purification except CHCl 3. The commercial purchased CHCl 3 was purified via wash by water and distillation to remove the stabilizer CH 3CH 2OH according to the standard methods. Analytical thin layer chromatography (TLC) was performed on precoated silica gel 60 F 254 plates. Visualization on TLC was achieved with UV light (254 nm) as the visualization method. Purification of the coupling products was performed by flash column chromatography using silica gel ( mesh). 1 H NMR spectra were recorded on a Bruker AVANCE III HD 400 (400 MHz) or a Bruker AVANCE III HD 500 (500 MHz). Chemical shifts were quoted in parts per million (ppm) referenced to 0.0 ppm for tetramethylsilane. Signal positions were recorded in δ ppm with the following abbreviations: s, d, t, q, sept, br, app, and m denoting singlet, doublet, triplet, quartet, septet, broad, apparent, and multiplet, respectively. 13 C NMR and DEPT-135 spectra were recorded on a Bruker AVANCE III HD 400 (101 MHz) or a Bruker AVANCE III HD 500 (126 MHz). Chemical shifts were reported in ppm referenced to the center line of a triplet at ppm of chloroform-d. Melting points were measured with an XT4A microscopic melting-point detector, produced by the Beijing Keyi Electro-optic Instrument Plant. 2. General Procedure for Bromination A typical bromination procedure (Table S2, entry 10). KBr (29.8 mg, 0.25 mmol, 1 equiv), CF 3CH 2OH (0.2 ml), cyclohexane (105.2 mg, 5 equiv), 40% NaNO 2 (4.3 mg, 3.0 μl, 10 mol %), 37% HCl (aq) (42 μl, 0.5 mmol, 2 equiv) were added to an oven-dried tube. The reaction tube was equipped with a magnetic stir bar and sealed with a Teflon-lined cap, and irradiated with a 23 W compact fluorescent light bulb ca. 10 cm distance at room temperature (20 30 C). The reaction mixture turned brownish orange and when it turns colorless, the reaction is finished. The reaction time of each reaction is shown in the tables. Notably, 37% HCl (aq) was the last reagent added, followed by the tube being sealed at once, to avoid HCl gas escaping. After the reaction was finished, the reaction mixture was extracted into CDCl 3 (2.0 ml) containing CH 2Br 2 as an internal standard, S2

3 added ca. 0.5 g anhydrous Na 2SO 4, stirred for 30 seconds and standing 10 minutes. The organic extracts were detected by 1 H NMR analysis. The extract could be concentrated, and the residue was purified by flash column chromatography on silica gel to give the product. A typical procedure on a larger scale to give the isolated yields (Table S5, entry 10). KBr (238.0 mg, 2 mmol, 1 equiv), NaNO 2 (13.8 mg, 0.2 mmol, 10 mol %), cyclooctane 1b (448.9 mg, 4 mmol, 2 equiv), CF 3CO 2H (147 μl, mg, 2 mmol, 1 equiv), 37% HCl (aq) (0.50 ml, mg, 6 mmol, 3 equiv) were added to a 250 ml round-bottom flask. The reaction flask was equipped with a magnetic stir bar and sealed with a ground glass stopper, and irradiated with a 16 W LED (equal to a 27 W CFL) ca. 10 cm distance at room temperature (20 30 C). The reaction mixture turned brownish orange. After 4 hours, it turned colorless meaning the reaction was finished. The reaction mixture was extracted with CH 2Cl 2 (3 5 ml), dried with anhydrous Na 2SO 4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, hexane) to give 2b (236.8 mg, 62%) as a colorless liquid. 3. Optimization for bromination of some substrates Table S1. Bromination of cyclohexane with various acids a entry H + (equiv) time (h) 2a yield (%) b 3a yield (%) b 1 c Bi(NO 3) 3 5H 2O (1) 24 trace M H 2SO 4 (1.1) 10 trace trace 3 5 M H 2SO 4 (1.2) d 5 M H 2SO 4 (1.2) e 5 M H 2SO 4 (1.2) M H 2SO 4 (2) %H 2SO 4 (2.3) f 40% HBr (1) CF 3CO 2H (2.2) S3

4 10 37% HCl (2) BiCl 3 (0.9) c 37% HCl (2) g 37% HCl (2) a Conditions: cyclohexane 1a (105.2 mg, 5 equiv), KBr (29.8 mg, 0.25 mmol, 1 equiv), 40% NaNO 2 (aq) (4.3 mg, 10 mol %), acid ( equiv), 23 W CFL, air, rt, in a 35 ml sealed tube. b Yields are based on KBr and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard. c Without NaNO 2. d NaNO 2 (5 mol %). e NaNO 3 instead of NaNO 2. f Without KBr. g N 2 instead of air. Table S2. Bromination of cyclohexane with different concentration of HCl (aq) a entry H + (equiv) additives time (h) 2a (%) b 3a (%) b 1 20% HCl (3.9) % HCl (2) c 37% HCl (2) % HCl (2) % HCl (3) % HCl (3.5) % HCl (3.5) % HCl (5) % HCl (2) diatomite (80 mg) % HCl (2) TFE (0.2 ml) % HCl (2) diatomite (80 mg) and TFE (0.2 ml) d 37% HCl (2) TFE (0.2 ml) c 37% HCl (2) TFE (0.2 ml) e 37% HCl (2) TFE (0.2 ml) f 37% HCl (2) TFE (0.2 ml) g 37% HCl (2) TFE (0.2 ml) h 37% HCl (2) TFE (0.2 ml) i 37% HCl (2) TFE (0.2 ml) j 37% HCl (2) TFE (0.2 ml) k a Conditions: cyclohexane 1a (105.2 mg, 5 equiv), KBr (29.8 mg, 0.25 mmol, 1 equiv), 40% NaNO 2 S4

5 (aq) (4.3 mg, 10 mol %), HCl (aq) (2 5 equiv), 23 W CFL at a distance of 10 cm, air, rt, in a 35 ml sealed tube. b Yields are based on KBr and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard. c NaNO 2 (5 mol %). d NaNO 2 (6.5 mol %). e 11 W CFL instead of 23 W CFL. f 4 W LED instead of 23 W CFL. g 30 W daylight lamp instead of 23 W CFL at a distance of 1.5 m. h 1a (21.0 mg, 1 equiv). i 1a (63.1 mg, 3 equiv). j 1a (168.3 mg, 8 equiv). k Cyclohexane 1a (420.8 mg, 5 mmol), KBr (119.0 mg, 1 mmol, 1 equiv), NaNO 2 (6.9 mg, 0.1 mmol, 10 mol %), TFE (0.8 ml), 37% HCl (aq) (170 μl, 2 mmol, 2 equiv), 16 W LED (equal to a 27 W CFL), O 2, rt, 26 h, in a 25 ml schlenk tube. For cyclohexane, the reaction required more O 2, more reaction time and stronger light when it was performed on a larger scale. Table S3. Bromination of cyclohexane with various solvents a entry solvent time (h) 2a yield (%) b 3a yield (%) b 1 TFE CH 2Cl CHCl CH 3NO PhCl PhNO ,3-dichlorobenzene benzene c 9 CH 3CN tbuoh TFE/CH 2Cl a Conditions: cyclohexane 1a (105.2 mg, 5 equiv), KBr (29.8 mg, 0.25 mmol, 1 equiv), 40% NaNO 2 (aq) (4.3 mg, 10 mol %), 37% HCl (aq) (42 μl, 2 equiv), solvent (0.2 ml), 23 W CFL at a distance of 10 cm, air, rt, in a 35 ml sealed tube. b Yields are based on KBr and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard. c Bromobenzene was detected by 1 H NMR analysis. S5

6 Table S4. Bromination of cyclohexane with various amount of cyclohexane a entry 1a (equiv) time (h) 2a yield (%) b 3a yield (%) b a Conditions: cyclohexane 1a ( mg), KBr (29.8 mg, 0.25 mmol, 1 equiv), 40% NaNO 2 (aq) (4.3 mg), 37% HCl (aq) (42 μl), 23 W CFL at a distance of 10 cm, air, rt, in a 35 ml sealed tube. b Yields are based on KBr and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard. Table S5. Bromination of cyclooctane under different conditions a entry 1b (equiv) H + (equiv) solvent time (h) 2b yield (%) b 1 4 HCl (2) TFE HCl (3) TFE HCl (2) HCl (3) HCl (4) HCl (3)+ TFA (1) 6 80 c 7 4 HCl (2)+ TFA (2) TFA (4) HCl (3)+ TFA (1) d 2 HCl (3)+ TFA (1) 4 (62) 11 2 HCl (3)+ TFA (1) CH 2Cl HCl (3)+ TFA (1) CHCl HCl (3)+ TFA (1) d 1 HCl (3)+ TFA (1) 4 (53) S6

7 15 1 HCl (3)+ TFA (1) CH 2Cl HCl (3)+ TFA (1) CHCl a Conditions: cyclooctane 1b ( mg), KBr (29.8 mg, 0.25 mmol, 1 equiv), 40% NaNO 2 (aq) (4.3 mg, 10 mol %), 37% HCl (aq) (21 84 μl), CF 3CO 2H (TFA) (20 80 μl), solvent (0.2 ml), 23 W CFL at a distance of 10 cm, air, rt, in a 35 ml sealed tube. b Yields are based on KBr and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard; yields in parentheses refer to isolated yields. c A byproduct chlorocyclooctane 20%. d On a larger scale to give the isolated yields, KBr (238.0 mg, 2 mmol, 1 equiv). Table S6. Bromination of cyclooctane with Br 2 a entry Br 2 (equiv) method time (h) 1 (%) NaNO 2 (10 mol %) NaNO 2 (10 mol %), HCl (2 equiv) NaNO 2 (10 mol %), HBr (0.5 equiv) a Conditions: cyclooctane 1b (28.1 mg, 0.25 mmol, 1 equiv), 40% NaNO 2 (aq) (4.3 mg, 10 mol %), Br 2 (8 wt% CHCl 3 stock solution, 250 or 125 mg), 37% HCl (aq) and 40% HBr (aq) (added as the amount shown in the table), 23 W CFL at a distance of 10 cm, air, rt, in a 35 ml sealed tube. Yields are based on KBr and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard. Notably, the Br 2 and NaNO 2 were added from solutions, an 8 wt% CHCl 3 solution and a 40 wt% aqueous solution respectively, for they were not easy to be accurately weighed. Table S7. Bromination of nitroethane under different conditions a entry Br (equiv) oxidation conditions b temp ( C) time (h) 2i (%) c 1 KBr (1) A rt Br 2 (0.5) A rt Br 2 (1) Br 2 (0.5) B rt d 5 KBr (1) B e S7

8 6 B rt 19 0 a Conditions: nitroethane 1i (56.3 mg, 0.75 mmol, 3 equiv), KBr (29.8 mg, 0.25 mmol, 1 equiv) or Br 2 (bromine 18.7 wt% chloroform solution, mg, equiv), CHCl 3 (0.2 ml), air, 23 W CFL, in a 35 ml sealed tube, rt 40 C, h. b Condition A: 40% NaNO 2 (aq) (4.3 mg, 10 mol %), 37% HCl (aq) (42 μl, 2 equiv); Condition B: Oxone (76.5 mg, 0.5 equiv), H 2O (90.0 mg, 20 equiv). c Yields are based on bromine atom and detected by 1 H NMR analysis using CH 2Br 2 as an internal standard. d A byproduct 1-bromo-1-nitroethane 3%. e A byproduct 1-bromo-1-nitroethane 4%. 4. Data bromocyclohexane (2a) 1 : Two of the same reaction mixture (in 0.25 mmol scale) were combined to obtain the isolated yield of the products. The reaction mixture was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, low boiling point (30 60 C) petroleum ether) to give 2a (49.8 mg, 61%) as a colorless liquid. 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 2H), (m, 4H), (m, 1H), (m, 3H). 13 C NMR (101 MHz, CDCl3) δ 53.76, 37.70, 26.02, DEPT-135 (101 MHz, CDCl3) δ (upward), (downward), (downward), (downward). 1,2-dibromocyclohexane (3a) 1 : Two of the same reaction mixture were combined to obtain the isolated yield of the products. The reaction mixture was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, low boiling point (30 60 C) petroleum ether) to give 3a (3.5 mg, 3%) as a colorless liquid. 1 H NMR (400 MHz, CDCl3) δ (m, 2H), (m, 2H), (m, 4H), (m, 2H). S8

9 13 C NMR (101 MHz, CDCl3) δ 55.34, 32.17, DEPT-135 (101 MHz, CDCl3) δ (upward), (downward), (downward). bromocyclooctane (2b) 2 : The reaction mixture (in 2 mmol scale) was extracted with CH2Cl2 (3 5 ml), dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, hexane) to give 2b (236.8 mg, 62%) as a colorless liquid. 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 2H), (m, 2H), (m, 2H), (m, 8H). 13 C NMR (101 MHz, CDCl3) δ 57.79, 36.07, 27.53, 25.10, DEPT-135 (101 MHz, CDCl3) δ (upward), (downward), (downward), (downward), (downward). bromocyclopentane (2c) 1 The boiling point of 2c is low. Two of the same reaction (in 0.25 mmol scale) mixture were combined. The reaction mixture was extracted with CH2Cl2 (3 2 ml), dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, low boiling point (30 60 C) petroleum ether) to give 2c (5.2 mg, 7%) as a colorless liquid. 1 H NMR (500 MHz, CDCl3) δ (m, 1H), (m, 4H), (m, 2H), (m, 2H) 13 C NMR (126 MHz, CDCl3) δ 54.14, 37.98, DEPT-135 (126 MHz, CDCl3) δ (upward), (downward), (downward). 1- bromoadamantane (2d1) 2 : white solid; m.p C (ref 3: S9

10 119 C). The reaction mixture (in 0.25 mmol scale) was extracted with CH2Cl2 (3 5 ml), dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, hexane) to give 2d (36.0 mg, 67%, 2d1: 2d2 = 2.4:1) as a white solid. The polarities of 2d1 and 2d2 are very close. They were saperated by column tomography of several times, but with great loss (2d1, 10.6 mg, 20%; 2d2, 9 mg, 17%). 1 H NMR (500 MHz, CDCl3) δ 2.37 (d, J = 2.5 Hz, 6H), 2.11 (s, 3H), 1.73 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 67.01, 49.46, 35.68, DEPT-135 (126 MHz, CDCl3) δ (downward), (downward), (upward). 2-bromoadamantane (2d2) 2 : isolated yield of 2d, 36.0 mg, 67% (2d1: 2d2 = 2.4:1); white solid; m.p. 135 C; sublimating easily if heated (ref 3: 139 C). 1 H NMR (400 MHz, CDCl3) δ 4.68 (s, 1H), 2.34 (d, J = 14.8 Hz, 2H), 2.14 (s, 2H), (m, 8H), 1.63 (d, J = 12.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 64.08, 38.81, 37.95, 36.48, 31.75, 27.62, DEPT-135 (101 MHz, CDCl3) δ (upward), (downward), (downward), (upward), (downward), (upward), (upward). 3-bromo-2,2-dimethylpropanenitrile (2e) 4 : colorless liquid. The reaction mixture (in 0.25 mmol scale) was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The residue was purified by silica column chromatography (17 mm 17 cm column, 10% CH2Cl2 in hexane) to give 2e (25.6 mg, 63%). 1 H NMR (500 MHz, CDCl3) δ 3.42 (s, 2H), 1.51 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ , 39.23, 34.51, DEPT-135 (126 MHz, CDCl3) δ (downward), (upward). S10

11 3-bromo-2,2-dimethylpropanoic acid (2f) 5 The reaction mixture (in 0.25 mmol scale) was dried with anhydrous Na2SO4, filtered and purified via rotary evaporation. 2f and 1f were hardly separated by silica column chromatography because of their strong and similar polarity. The mixture of 2f and 1f is a colorless solid. Isolated yield of 2f: 80% (the mixture of 2f and 1f was obtained 67.5 mg, 2f:1f = 1:1.53). 1 H NMR (400 MHz, CDCl3) δ (brs, 1H), 3.52 (s, 2H), 1.36 (s, 6H). 13 C NMR (101 MHz, CDCl3) δ , 44.10, 40.67, DEPT-135 (101 MHz, CDCl3) δ (downward), (upward). 1-bromo-2-methyl-2-nitropropane (2g) 2 The reaction mixture (in 0.25 mmol scale) was dried with anhydrous Na2SO4, filtered and purified via rotary evaporation. The mixture of 2g and 1g is a colorless oil. Isolated yield of 2g: 23.0 mg, 51% (purity 85%). 1 H NMR (500 MHz, CDCl3) δ 3.78 (s, 2H), 1.74 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 87.18, 37.93, DEPT-135 (126 MHz, CDCl3) δ (downward), (upward). 1-bromo-3-nitropropane (2h1) 2 : yellowish transparent liquid. The reaction mixture (in 0.25 mmol scale) was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The product was purified by silica column chromatography (17 mm 17 cm column, 20% CH2Cl2 in low boiling point (30 60 C) petroleum ether) to give 2h1 (19.1 mg, 45%). 1 H NMR (400 MHz, CDCl3) δ 4.59 (t, J = 6.4 Hz, 2H), 3.51 (t, J = 6.0 Hz, 2H), (m, 2H). 13 C NMR (101 MHz, CDCl3) δ 73.31, 29.89, DEPT-135 (101 MHz, CDCl3) δ (downward), (downward), (downward). S11

12 2-bromo-1-nitropropane (2h2) 2 : yellowish transparent liquid. The reaction mixture (in 0.25 mmol scale) was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The product was purified by silica column chromatography (17 mm 17 cm column, 10% CH2Cl2 in low boiling point (30 60 C) petroleum ether) to give 2h2 (4.3 mg, 10%). 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 2H),1.80 (d, J = 5.6 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 81.93, 39.94, DEPT-135 (101 MHz, CDCl3) δ (downward), (upward), (upward). 1-bromo-2-nitroethane (2i) 6 : colorless liquid; Two of the same reaction mixture were combined to obtain the isolated yield of the products. The reaction mixture (in 0.5 mmol scale) was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The product was purified by silica column chromatography (17 mm 17 cm column, 25% CH2Cl2 in low boiling point (30 60 C) petroleum ether) to give 2i (4.0 mg, 5%). 1 H NMR (500 MHz, CDCl3) δ 4.77 (t, J = 6.5 Hz, 2H), 4.02 (t, J = 6.5 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 75.67, DEPT-135 (126 MHz, CDCl3) δ (downward), (downward). 3-bromopropanoic acid (2j1) 2 The reaction mixture (in 0.25 mmol scale) was dried with anhydrous Na2SO4, filtered. The product was purified via rotary evaporation. 2j and 1j were hardly separated by silica column chromatography because of their strong and similar polarity. the mixture of 2j and 1j is a colorless liquid. Isolated yield of 2j1: 65% (the mixture of 2j, 1j and 3j was obtained 72.2 mg, mole ratio 2j1:2j2:1j:3j = 1:0.35:2.62:0.40). 1 H NMR (400 MHz, CDCl3) δ (brs, 1H), 3.58 (t, J = 6.8 Hz, 2H), 2.99 (t, J = 6.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ , 37.61, S12

13 DEPT-135 (101 MHz, CDCl3) δ (downward), (downward). 2-bromopropanoic acid (2j2) 2 Isolated yield of 2j2: 23% (the mixture of 2j, 1j and 3j was obtained 72.2 mg, mole ratio 2j1:2j2:1j:3j = 1:0.35:2.62:0.40).. 1 H NMR (400 MHz, CDCl3) δ (brs, 1H), 4.40 (q, J = 7.2 Hz, 1H), 1.85 (d, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ , 39.75, DEPT-135 (101 MHz, CDCl3) δ (upward), (upward). 2-bromohexane (2k1) 7 The reaction mixture (in 0.25 mmol scale) was dried with anhydrous Na2SO4, filtered and purified via rotary evaporation to give 2k (13.6 mg, 33%, 2k1:2k2 = 1.4:1) as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 2H), 1.70 (d, J = 6.4 Hz, 3H), (m, 4H), 0.93 (t, J = 6.4 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 51.91, 41.13, 30.14, 26.60, 22.30, DEPT-135 (101 MHz, CDCl3) δ (upward), (downward), (downward), (upward), (downward), (upward). 3-bromohexane (2k2) 7 The reaction mixture (in 0.25 mmol scale) was dried with anhydrous Na2SO4, filtered and purified via rotary evaporation to give 2k (13.6 mg, 33%, 2k1:2k2 = 1.4:1) as a colorless oil. 1 H NMR (400 MHz, CDCl3) δ (m, 1H), (m, 4H), (m, 2H), 1.04 (t, J = 7.2 Hz, 3H), 0.91 (t, J = 6.8 Hz, 3H). 13 C NMR (101 MHz, CDCl3) δ 60.31, 41.06, 32.40, 21.04, 13.60, DEPT-135 (101 MHz, CDCl3) δ (upward), (downward), (downward), (downward), (upward), (upward). S13

14 1-(bromomethyl)-4-nitrobenzene (2l) 8 : white solid; m.p C (ref 8: C). The product 2l was purified by silica column chromatography (17 mm 17 cm column, gradient of 0% to 2%, EA in hexane) to give 2l (41.6 mg, 77%). 1 H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 4.52 (s, 2H). 13 C NMR (101 MHz, CDCl3) δ , , , , DEPT-135 (101 MHz, CDCl3) δ (upward), (upward), (downward). (bromomethyl)benzene (2m) 9 1 H NMR (400 MHz, CDCl3) δ (m, 5H), 4.50 (s, 2H). 13 C NMR (101 MHz, CDCl3) δ 137.9, 129.2, 128.9, 128.6, The reaction mixture (in 0.25 mmol scale) was extracted with CH2Cl2 (3 3 ml), dried with anhydrous Na2SO4, filtered and concentrated. The products were purified by silica column chromatography (17 mm 17 cm column, 1% EA in hexane) to give 2m/4m (25.2 mg, 59%, 2m:4m1:4m2 = 2.8:1.1:1) as a light yellow liquid. Isolated yield of 2m: 34%. 1-bromo-2-methylbenzene (4m1) 10 Isolated yield of 4m1: 13% (total products, 25.2 mg, 2m:4m1:4m2 = 2.8:1.1:1). 1 H NMR (400 MHz, CDCl3) δ 7.52 (d, J = 8.0 Hz, 1H), (m, 2H), (m, 1H), 2.40 (s, 3H). 1-bromo-4-methylbenzene (4m2) 10 S14

15 Isolated yield of 4m2: 12% (total products, 25.2 mg, 2m:4m1:4m2 = 2.8:1.1:1). 1 H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 8.4 Hz, 2H), 7.04 (d, J = 8.4 Hz, 2H), 2.30 (s, 3H). 5. References (1) Li, Y.; Ju, J.; Jia, J.; Sheng, W.; Han, L.; Gao, J. Chin. J. Chem. 2010, 28, (2) Integrated Spectral Database System of Organic Compounds. (Data were obtained from the National Institute of Advanced Industrial Science and Technology (Japan)) (Read from scifinder). (3) Olah, G. A.; Welch, J. T.; Vankar, Y. D.; Nojima, M.; Kerekes, I.; Olah, J. A. J. Org. Chem. 1979, 44, (4) Schunk, S.; Reich, M.; Koenigs, R. M. WO Oct 7, (5) Brücher, O.; Hartung, J. ACS Catal. 2011, 1, (6) Ranganathan, D.; Ranganathan, S.; Bamezai, S.; Mehrotra, S.; Ramachandran, PV. J. Chem. Res. (S), 1983, (7) Wirth, T.; Montoro, R. Synthesis 2005, (8) Podgoršek, A.; Stavber, S.; Zupan, M.; Iskra, J. Tetrahedron, 2009, 65, (9) Cantillo, D.; de Frutos, O.; Rincon, J. A. Mateos, C.; Kappe, C. O. J. Org. Chem. 2014, 79, (10) Yang, C.-T.; Zhang, Z.-Q.; Liu, Y.-C.; Liu, L. Angew. Chem. Int. Ed. 2011, 50, S15

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