Supporting Information

Supporting Information Copper-Catalyzed Aerobic Oxidative Intramolecular C-H Amination Leading to Imidazobenzimidazole Derivatives Xiaoqiang Wang, Yunhe Jin, Yufen Zhao,, Lin Zhu, and Hua Fu *, Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University, Beijing 100084, P. R. China Key Laboratory for Chemical Biology of Fujian Province, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China Department of Chemical Engineering, Tsinghua University, Beijing 100084, P. R. China E-mail: fuhua@mail.tsinghua.edu.cn Table of contents General experimental procedures General procedure for synthesis of compounds IIa-d General procedure for synthesis of compounds 1a-f and 1i-w General procedure for synthesis of compounds 1g-h General procedure for synthesis of compounds 1x Characterization data of compounds 1a-x General procedure for synthesis of compounds 2a-x Characterization data of compounds 2a-x Crystal preparation and X-ray diffraction analysis of compound 2m References The 1 H and 13 C NMR spectra of compounds 1a-x The 1 H and 13 C NMR spectra of compounds 2a-x S2 S2 S3 S3 S3 S4 S13 S14 S24 S29 S30 S78 -S1 -

General experimental procedures Proton and carbon magnetic resonance spectra ( 1 H NMR and 13 C NMR) were recorded on a JOEL JNM-ECA300 spectrometer with 300.0 and 75.0 MHz, respectively, using tetramethylsilane (TMS) in the solvent of CDCl 3 as the internal standard ( 1 H NMR: TMS at 0.00 ppm, CDCl 3 at 7.26 ppm; 13 C NMR: CDCl 3 at 77.0 ppm). Low resolution mass spectra (ESI-MS) were performed on a ESQUIR-LC mass spectrometer, and high resolution mass spectra (HRMS) were performed on a Bruker En Apexultra 7.0 FT-MS mass spectrometer. X-ray diffraction analysis was carried out on a R-AXIX SPIDER diffractometer. Compounds 1a-w were prepared according to the previous references. 1-4 R 2 CuI, K F 2 CO 3, DMF HN R 1 + R 2 N N 110 o C, N 2 R 1 NO 2 N 90-95% NO Ref. (1) 2 Ia-d Pd/C, H 2 ethanol, rt 97-99% Ref. (2) R 2 N N R 1 NH 2 I R' CuI, K 3 PO 4 THF, 110 o C path A 23-60% Ref. (3) R 1 1a-d 1i-w R 2 N N NH R' R 2 IIa-d R 3 CHO, TFA path B 55-60% Ref. (4) -S2 - R 1 1g-h Scheme 1. Synthetic route for compounds 1a-w General procedure for synthesis of compounds IIa-d. 1,2 An oven-dried 100 ml round-bottomed flask with a magnetic stirring bar was charged with CuI (1 mol, 19 mg), K 2 CO 3 (12 mmol, 1.66 g), substituted 1H-imidazole or 1H-benzo[d]imidazole (12 mmol), substituted 1-fluoro-2-nitrobenzene (10 mmol), and DMF (10 ml) under nitrogen. The mixture was stirred for 24 h at 110 o C. The resulting solution was then cooled to room temperature and filtered. The solid was washed with ethyl acetate for three times (3 10 ml), and the combined filtrate was concentrated by the rotary evaporator, and the residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (1:1) as eluent to give I. Palladium-on-charcoal N NH R 3 N

(10%, 0.27 g) was carefully added to a solution of I (10.6 mmol) in ethanol (150 ml), and I was hydrogenated at medium pressure (3 atm) and ambient temperature for 4 h. The resulting solution was filtered through a Celite pad and washed thoroughly with ethanol. The solvent was removed under reduced pressure to give amine IIa-d as a brown solid (97-99%). General procedure for synthesis of compounds 1a-f and 1i-w. Compounds 1a-f and 1i-w were prepared using the modified procedure. 3 IIa-d (4 mmol), CuI (0.4 mmol, 78 mg), potassium phosphate (4 mmol, 414 mg), substituted iodobenzene (2 mmol) and tetrahydrofuran (2 ml) were added to a Schlenk tube. The reaction was performed at 110 o C for 24 under nitrogen, and the resulting mixture was cooled to room temperature and filtered. The solid was washed with ethyl acetate for three times (3 7 ml), and the combined filtrate was concentrated by the rotary evaporator, and the residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (3:1) as eluent to give 1a-f and 1i-w. General procedure for synthesis of compounds 1g-h. 4 A solution of aldehyde (1 mmol) and TFA (2 ml) was magnetically stirred at 35 40 o C. After 5 min, IIa-d (1 mmol) was added, and the mixture was vigorously stirred. After 5 min, NaBH 4 (1.2 mmol) was added, and the progress of the reaction was monitored by TLC (petroleum ether/etoac, 5:1). After completion of the reaction, the solution was neutralized with saturated aqueous NaHCO 3 and extracted with ethyl acetate three times (3 5 ml). The combined organic layer was dried over anhydrous Na 2 SO 4 and concentrated under vacuum, and the residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (5:1) as eluent to give 1g-h. Synthesis of compound 1x. 1 An oven-dried 25 ml round-bottomed flask with a magnetic stirring bar was charged with CuI (0.1 mmol, 19 mg), K 2 CO 3 (2 mmol, 280 mg), 2-(5,6-dimethyl-1H-benzo[d]imidazol-1-yl)benzenamine (IId) (1.2 mmol, 284 mg), 1-fluoro-2-nitrobenzene (1 mmol, 141 mg), and DMF (2 ml) under nitrogen. The mixture was stirred for 24 h at 110 o C. The resulting solution was then cooled to room temperature and filtered. The solid was washed with ethyl acetate for three times (3 10 ml), and the combined filtrate was concentrated by the rotary evaporator, -S3 -

and the residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (3:1) as eluent to give 1x. N-(2-(1H-imidazol-1-yl)phenyl)benzenamine (1a). Eluent: petroleum ether/ethyl acetate (3:1). Yield 127 mg (27%), white solid, mp 156-158 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.62 (s, 1H), 7.41-6.91 (m, 11H), 5.84 (s, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 141.9, 139.4, 137.9, 130.2, 129.6, 129.5, 127.5, 126.3, 122.5, 120.7, 120.3, 119.7, 117.5. ESI-MS: [M+H] + m/z 236.2, [M+Na] + m/z 258.1. N-(2-(1H-Imidazol-1-yl)phenyl)-4-methylbenzenamine (1b). Eluent: petroleum ether/ethyl acetate (3:1). Yield 125 mg (25%), white solid, mp 162-163 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.64 (s, 1H), 7.29-7.06 (m, 7H), 7.02-6.85 (m, 3H), 5.63 (s, 1H), 2.31 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 140.3, 138.9, 137.9, 132.6, 130.2, 130.1, 129.7, 127.5, 125.5, 120.9, 120.3, 119.9, 116.3, 20.9. ESI-MS: [M+H] + m/z 250.3, [M+Na] + m/z 272.1. N-(2-(1H-Imidazol-1-yl)phenyl)-3-methylbenzenamine (1c). Eluent: petroleum ether/ethyl acetate (3:1). Yield 150 mg (30%), white solid, mp 114-116 o C. 1 H NMR -S4 -

(CDCl 3, 300 MHz) δ 7.61 (s, 1H), 7.42-7.10 (m, 6H), 6.99-6.79 (m, 4H), 5.92 (s, 1H), 2.31 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.0, 139.5, 137.8, 130.2, 129.6, 129.4, 127.4, 126.3, 123.4, 123.3, 120.6, 120.3, 117.7, 117.4, 116.6, 21.6. ESI-MS: [M+H] + m/z 250.3, [M+Na] + m/z 272.1. N-(2-(1H-Imidazol-1-yl)phenyl)-3,5-dimethylbenzenamine (1d). Eluent: petroleum ether/ethyl acetate (3:1). Yield 163 mg (31%), white solid, mp 158-160 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.61 (s, 1H), 7.40-7.08 (m, 5H), 6.97-6.89 (s, 1H), 6.72-6.60 (m, 3H), 5.64 (s, 1H), 2.25 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 141.7, 139.5, 139.3, 137.8, 130.2, 129.6, 127.4, 126.2, 124.4, 120.4, 120.3, 117.6, 117.4, 21.5. ESI-MS: [M+H] + m/z 264.3, [M+Na] + m/z 286.1. N-(2-(1H-Imidazol-1-yl)phenyl)-4-methoxylbenzenamine (1e). Eluent: petroleum ether/ethyl acetate (3:1). Yield 154 mg (29%), white solid, mp 148-150 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.66 (s, 1H), 7.29-7.00 (m, 7H), 6.91-6.81 (m, 3H), 5.37 (s, 1H), 3.79 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 156.4, 141.5, 138.0, 133.9, 133.8, 130.3, 129.8, 127.5, 127.4, 124.3, 120.4, 119.0, 114.9, 55.6. ESI-MS: [M+H] + m/z 266.2, [M+Na] + m/z 288.1. -S5 -

N-(2-(1H-Imidazol-1-yl)phenyl)-4-chlorolbenzenamine (1f). Eluent: petroleum ether/ ethyl acetate (3:1). Yield 124 mg (23%), white solid, mp 177-179 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.59 (s, 1H), 7.34-7.08 (m, 7H), 7.02-6.95 (m, 3H), 5.87 (s, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 140.7, 138.9, 137.8, 130.3, 129.7, 129.5, 127.6, 127.2, 126.6, 121.2, 120.7, 120.3, 117.8. ESI-MS: [M+H] + m/z 270.2, [M+Na] + m/z 292.1. N-Butyl-2-(1H-imidazol-1-yl)aniline (1g). Eluent: petroleum ether/ethyl acetate (5:1).Yield 119 mg (55%), white solid, mp 48-50 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.55 (s, 1H), 7.30-7.15 (m, 2H), 7.06-6.97 (m, 2H), 6.78-6.59 (m, 2H), 3.80-3.70 (m, 1H), 3.11-3.03 (m, 2H), 1.60-1.48 (m, 2H),1.47-1.28 (m, 2H), 0.90 (m, J = 14.8 Hz, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 143.7, 137.8, 130.0, 129.9, 127.0, 122.8, 120.2, 116.2, 111.4, 43.1, 31.2, 20.2, 13.8. ESI-MS: [M+H] + m/z 216.5, [M+Na] + m/z 238.3. 2-(1H-Imidazol-1-yl)-N-pentylaniline (1h). Eluent: petroleum ether/ethyl acetate (5:1). Yield 138 mg (60%), white solid, mp 57-59 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.51 (s, 1H), 7.21-7.15 (m, 2H), 7.00-6.97 (m, 2H), 6.68-6.62 (m, 2H), 3.47 (s, 1H), -S6 -

3.02-2.96 (m, 2H), 1.46-1.43 (m, 2H), 1.23-1.18 (m, 4H), 0.82-0.79 (m, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 143.8, 138.0, 130.2, 130.1, 127.2, 122.9, 120.4, 116.4, 111.5, 43.5, 29.2, 28.9, 22.4, 14.1. ESI-MS: [M+H] + m/z 230.5, [M+Na] + m/z 252.4. N-(2-(1H-Imidazol-1-yl)-4-methylphenyl)benzenamine (1i). Eluent: petroleum ether/ ethyl acetate (5:1). Yield 150 mg (30%), white solid, mp 164-166 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.65 (s, 1H), 7.33-7.03 (m, 7H), 7.01-6.91 (m, 3H), 5.36 (s, 1H), 2.34 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.6, 137.8, 136.1, 131.3, 130.2, 130.1, 129.5, 127.7, 127.0, 121.9, 120.3, 118.9, 118.5, 20.5. ESI-MS: [M+H] + m/z 250.4, [M+Na] + m/z 272.2. N-(2-(1H-Imidazol-1-yl)-4-methylphenyl)-4-methylbenzenamine (1j). Eluent: petroleum ether/ethyl acetate (5:1). Yield 185 mg (35%), white solid, mp 169-171 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.56 (s, 1H), 7.21-6.87 (m, 7H), 6.85-6.73 (m, 2H), 5.31 (s, 1H), 2.23 (s, 3H), 2.20 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 139.8, 137.8, 137.0, 131.8, 130.4, 130.1, 130.0, 127.7, 126.2, 120.4, 119.6, 117.8, 20.8, 20.4. ESI-MS: [M+H] + m/z 264.2, [M+Na] + m/z 286.1. -S7 -

N-(2-(1H-Imidazol-1-yl)-4-methylphenyl)-3-methylbenzenamine (1k). Eluent: petroleum ether/ethyl acetate (5:1). Yield 274 mg (52%), white solid, mp 139-141 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.63 (s, 1H), 7.34-7.00 (m, 6H), 6.84-6.68 (m, 3H), 5.36 (s, 1H), 2.33 (s, 3H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.6, 139.5, 137.7, 136.1, 131.2, 130.1, 130.0, 129.3, 127.7, 127.0, 122.7, 119.2, 119.0, 115.5, 21.6, 20.5. ESI-MS: [M+H] + m/z 264.2, [M+Na] + m/z 286.1 N-(2-(1H-Imidazol-1-yl)-4-methylphenyl)-3,5-dimethylbenzenamine (1l). Eluent: petroleum ether/ethyl acetate (5:1). Yield 333 mg (60%), white solid, mp 189-191 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.62 (s, 1H), 7.35-7.01 (m, 5H), 6.65-6.55 (m, 3H), 5.33 (s, 1H), 2.33 (s, 3H), 2,24 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 142.6, 139.2, 137.7, 136.2, 131.0, 130.1, 130.0, 127.6, 127.0, 123.6, 120.3, 119.2, 116.2, 21.5, 20.5. ESI-MS: [M+H] + m/z 278.3, [M+Na] + m/z 300.1. N-(4-Chlorophenyl)-2-(1H-imidazol-1-yl)-4-methylaniline (1m). Eluent: petroleum ether/ethyl acetate (5:1). Yield 278 mg (49%), white solid, mp 172-174 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.61 (s, 1H), 7.28-7.04 (m, 7H), 6.94-6.87 (m, 2H), 5.54 (s, 1H), 2.34 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 141.5, 137.6, 135.6, 132.1, 130.2, 130.1, 129.5, 127.8, 127.5, 126.3, 120.2, 119.4, 119.3, 20.6. ESI-MS: [M+H] + m/z 284.2, [M+Na] + m/z 306.0. -S8 -

2-(1H-Benzo[d]imidazol-1-yl)-N-phenylaniline (1n). Eluent: petroleum ether/ethyl acetate (5:1). Yield 131 mg (23%), white solid, mp 232-234 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.93 (s, 1H), 7.77 (s, 1H), 7.54-6.89 (m, 12H), 5.83 (s, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 143.4, 141.5, 140.4, 134.1, 130.1, 129.5, 129.0, 128.6, 123.9, 123.8, 123.0, 122.8, 120.5, 120.4, 120.2, 116.9, 110.8. ESI-MS: [M+H] + m/z 286.3, [M+Na] + m/z 308.1. 2-(1H-Benzo[d]imidazol-1-yl)-N-p-tolylaniline (1o). Eluent: petroleum ether/ethyl acetate (5:1). Yield 198 mg (33%), white solid, mp 209-211 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.89-7.70 (m, 2H), 7.42-6.88 (m, 11H), 5.79 (s, 1H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 143.6, 143.4, 141.2, 138,7, 134.1, 132.5, 130.1, 128.5, 123.8, 123.1, 122.9, 121.2, 120.4, 119.8, 116.0, 110.9, 20.9. ESI-MS: [M+H] + m/z 300.2, [M+Na] + m/z 322.1. -S9 -

2-(1H-Benzo[d]imidazol-1-yl)-N-m-tolylaniline (1p). Eluent: petroleum ether/ethyl acetate (5:1). Yield 221 mg (37%), white solid, mp 171-173 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.88 (s, 1H), 7.78 (s, 1H), 7.55-7.10 (m, 7H), 7.03-6.78 (m, 4H), 5.98 (s, 1H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 143.6, 143.3, 141.5, 140.5, 139.4, 134.0, 130.0, 129.3, 128.5, 123.9, 123.5, 122.9, 120.8, 120.4, 117.2, 117.1, 110.9, 21.6. ESI-MS: [M+H] + m/z 300.2, [M+Na] + m/z 322.1. N-(2-(1H-Benzo[d]imidazol-1-yl)phenyl)-3,5-dimethylaniline (1q). Eluent: petroleum ether/ethyl acetate (5:1). Yield 244 mg (39%), white solid, mp 184-186 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.98 (s, 1H), 7.88-7.80 (m, 1H), 7.53-7.17 (m, 6H), 7.03-6.94 (m, 1H), 6.70-6.60 (m, 3H), 5.46 (s, 1H), 2.23 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 143.7, 143.4, 141.1, 140.5, 139.2, 134.1, 130.0, 128.5, 124.7, 124.0, 123.6, 122.9, 120.6, 120.3, 117.9, 117.0, 110.8, 21.4. ESI-MS: [M+H] + m/z 314.3, [M+Na] + m/z 336.1. 2-(1H-Benzo[d]imidazol-1-yl)-N-(4-chlorophenyl)aniline (1r). Eluent: petroleum ether/ethyl acetate (5:1). Yield 166 mg (26%), white solid, mp 231-233 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.83 (s, 1H), 7.72-7.64 (m, 1H), 7.48-7.34 (m, 2H), 7.29-7.17 (m, 6H), 7.08-6.98 (m, 3H), 6.10 (s, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 143.5, 143.2, -S10 -

140.4, 140.0, 133.9, 130.1, 129.5, 128.7, 127.3, 124.2, 123.9, 123.0, 121.1, 121.0, 117.3, 110.7. ESI-MS: [M+H] + m/z 320.3, [M+Na] + m/z 342.1. 2-(5,6-Dimethyl-1H-benzo[d]imidazol-1-yl)-N-phenylaniline (1s). Eluent: petroleum ether/ethyl acetate (5:1). Yield 188 mg (30%), white solid, mp 188-190 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.81 (s, 1H), 7.55-7.40 (m, 2H), 7.40-7.18 (m, 4H), 7.09-6.92 (m, 5H), 5.91 (s, 1H), 2.33 (s, 3H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.6,142.2, 141.7, 140.5, 133.1, 132.7, 131.8, 129.9, 129.5, 128.5, 124.2, 122.6, 120.5, 120.4, 120.2, 116.9, 110.8, 20.5, 20.3. ESI-MS: [M+H] + m/z 314.3, [M+Na] + m/z 336.1. 2-(5,6-Dimethyl-1H-benzo[d]imidazol-1-yl)-N-p-tolylaniline (1t). Eluent: petroleum ether/ethyl acetate (5:1). Yield 229 mg (35%), white solid, mp 201-203 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.87 (s, 1H), 7.56 (s, 1H), 7.38-7.28 (m, 2H), 7.27-7.18 (m, 1H), 7.12-6.88 (m, 6H), 5.58 (s, 1H), 2.36 (s, 3H), 2.31 (s, 3H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.6, 142.2, 141.2, 138.6, 133.1, 132.8, 131.8, 130.0, 129.9, 128.5, 123.4, 121.3, 120.5, 119.7, 115.8, 110.8, 20.9, 20.6, 20.3. ESI-MS: [M+H] + m/z 328.2, [M+Na] + m/z 350.2. -S11 -

2-(5,6-Dimethyl-1H-benzo[d]imidazol-1-yl)-N-m-tolylaniline (1u). Eluent: petroleum ether/ethyl acetate (5:1). Yield 242 mg (37%), white solid, mp 145-147 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.86 (s, 1H), 7.55 (s, 1H), 7.49-7.31 (m, 2H), 7.26-6.94 (m, 4H), 6.91-6.77 (m, 3H), 5.66 (s, H), 2.35 (s, 3H), 2.30 (s, 3H), 2.27 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.7, 141.5, 140.5, 139.4, 133.2, 131.8, 129.9, 129.3, 128.5, 124.1, 123.6, 121.0, 120.5, 120.3, 117.3, 116.9, 110.8, 21.5, 20.6, 20.3. ESI-MS: [M+H] + m/z 328.2, [M+Na] + m/z 350.1. N-(2-(5,6-Dimethyl-1H-benzo[d]imidazol-1-yl)phenyl)-3,5-dimethylaniline (1v). Eluent: petroleum ether/ethyl acetate (5:1). Yield 246 mg (36%), white solid, mp 171-173 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.87 (s, 1H), 7.57 (s, 1H), 7.49-7.28 (m, 2H), 7.27-7.19 (m, 1H), 7.08-6.93 (m, 2H), 6.71-6.60 (m, 3H), 5.57 (s, 1H), 2.36 (s, 3H), 2.31 (s, 3H), 2.23 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 142.6 141.4, 140.6, 139.2, 133.1, 131.8, 129.8, 128.5, 124.6, 124.0, 120.5, 120.2, 118.0, 117.0, 110.9, 21.4, 20.6, 20.3. ESI-MS: [M+H] + m/z 342.3, [M+Na] + m/z 364.2. -S12 -

N-(4-Chlorophenyl)-2-(5,6-dimethyl-1H-benzo[d]imidazol-1-yl)aniline (1w). Eluent: petroleum ether/ethyl acetate (5:1). Yield 195 mg (28%), white solid, mp 183-185 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.81 (s, 1H), 7.53-7.30 (m, 3H), 7.30-7.10 (m, 3H), 7.08-6.92 (m, 4H), 5.90 (s, 1H), 2.33 (s, 3H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 142.4, 140.5, 140.0, 133.1, 132.5, 131.9, 129.9, 129.5, 128.6, 127.2, 124.5, 120.9, 120.3, 117.3, 110.7, 20.5, 20.3. ESI-MS: [M+H] + m/z 348.2, [M+Na] + m/z 370.0. N-(2-Nitrophenyl)-2-(5,6-dimethyl-1H-benzo[d]imidazol-1-yl)aniline (1x). Eluent: petroleum ether/ethyl acetate (5:1). Yield 183 mg (51%), yellow liquid. 1 H NMR (CDCl 3, 300 MHz) δ 9.00 (s, 1H), 8.00-7.90 (m, 2H), 7.78-7.73 (m, 1H), 7.33 (s, 1H), 7.35-7.16 (m, 5H), 6.93-6.87 (m, 1H), 6.69-6.61 (m, 1H), 2.33 (s, 3H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 143.4, 142.8, 142.2, 139.1, 136.3, 135.6, 134.0, 133.5, 132.1, 129.1, 128.8, 128.1, 126.5, 123.8, 122.8, 120.6, 118.1, 115.8, 110.2, 19.8, 19.5. ESI-MS: [M+H] + m/z 359.2, [M+Na] + m/z 381.0. General procedure for synthesis of compounds 2a-x. Substituted 2-(1H-imidazol-1-yl)-N-alkylbenzenamine (1) (0.3 mmol), Cu(OAc) 2 (0.06 mmol, 11 mg), 1,10-phenanthroline monohydrate (0.12 mmol, 23.5 mg), sodium acetate (1.2 -S13 -

mmol, 110 mg) and m-xylene (1 ml) were added to a Schlenk tube. The reaction was performed at 155 o C for 24 or 55 h using an oxygen balloon (1 atm), and the resulting mixture was cooled to room temperature and filtered. The solid was washed with ethyl acetate for three times (3 5 ml), and the combined filtrate was concentrated by the rotary evaporator, and the residue was purified by column chromatography on silica gel using petroleum ether/ethyl acetate (5:1) as eluent to give the desired product (2). 9-Phenylimidazo[1,2-a]benzimidazole (2a). Eluent: petroleum ether/ethyl acetate (5:1). Yield 65 mg (93%), yellow solid, mp 115-117 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.80 (d, J = 7.6 Hz, 2H), 7.59-7.52 (m, 4H), 7.42-7.18 (m, 5H). 13 C NMR (CDCl 3, 75 MHz) δ 149.0, 136.0, 135.0, 131.5, 129.9, 126.8, 125.0, 123.7, 123.6, 121.3, 111.3, 111.1, 106.4. HRMS (ESI) Calcd for C 15 H 12 N 3 [M+H] + 234.1031, found 234.1033. 9-(4-Methylphenyl)imidazo[1,2-a]benzimidazole (2b). Eluent: petroleum ether/ethyl acetate (5:1). Yield 69 mg (93%), white solid, mp 107-109 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.66 (d, J = 8.3 Hz, 2H), 7.58-7.49 (m, 2H), 7.41-7.42 (m, 3H), 7.30-7.16 (m, 3H), 2.42 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 149.2, 136.8, 135.2, 133.3, 131.5, 130.4, 124.9, 123.7, 123.5, 121.0, 111.2, 111.0, 106.3, 21.2. HRMS (ESI) Calcd for C 16 H 14 N 3 [M+H] + 248.1188, found 248.1188. -S14 -

9-(3-Methylphenyl)imidazo[1,2-a]benzimidazole (2c). Eluent: petroleum ether/ethyl acetate (5:1). Yield 69 mg (95%), yellow liquid. 1 H NMR (CDCl 3, 300 MHz) δ 7.60 (s, 1H), 7.58-7.47 (m, 3H), 7.44-7.34 (m, 2H), 7.27-7.12 (m, 4H), 2.44 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 149.0, 140.0, 135.8, 135.1, 131.5, 129.6, 127.8, 124.9, 124.4, 123.5, 121.1, 120.9, 111.2, 111.1, 106.3, 21.7. HRMS (ESI) Calcd for C 16 H 14 N 3 [M+H] + 248.1188, found 248.1177. 9-(3,5-Dimethylphenyl)imidazo[1,2-a]benzimidazole (2d). Eluent: petroleum ether/ethyl acetate (5:1). Yield 73 mg (93%), white solid, mp 133-135 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.41-7.36 (m, 2H), 7.26-7.23 (m, 3H), 7.18-7.01 (m, 3H), 6.87 (s, 1H), 2.28 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 149.1, 139.6, 135.7, 135.3, 131.5, 128.8, 124.9, 123.5, 121.7, 121.0, 111.2, 111.1, 106.2, 21.5. HRMS (ESI) Calcd for C 17 H 16 N 3 [M+H] + 262.1344, found 262.1341. 9-(4-Methoxyphenyl)imidazo[1,2-a]benzimidazole (2f). Eluent: petroleum ether/ethyl acetate (5:1). Yield 73 mg (93%), yellow solid, mp 121-123 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.65 (d, J = 8.9 Hz, 2H), 7.54 (d, J = 7.9 Hz, 1H), 7.44 (d, J = -S15 -

7.9, 1H), 7.40 (s, 1H), 7.28-7.16 (m, 3H), 7.06 (d, J = 8.9 Hz, 2H), 3.85 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 158.5, 149.4, 135.5, 131.5, 128.6, 125.6, 124.8, 123.5, 120.9, 115.1, 111.2, 110.8, 106.3, 55.7. HRMS (ESI) Calcd for C 16 H 14 N 3 O [M+H] + 264.1137, found 264.1137. 9-(4-Chlorophenyl)imidazo[1,2-a]benzimidazole (2f). Eluent: petroleum ether/ethyl acetate (5:1). Yield 74 mg (92%), white solid, mp 174-175 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.75 (d, J = 8.8 Hz, 2H), 7.59-7.45 (m, 4H), 7.38 (s, 1H), 7.32-7.20 (m, 2H), 7.18 (s, 1H). 13 C NMR (CDCl 3, 75 MHz) δ 148.6, 134.6, 134.5, 132.1, 131.5, 130.0, 125.0, 124.7, 123.7, 121.6, 111.4, 111.0, 106.6. HRMS (ESI) Calcd for C 15 H 11 ClN 3 [M+H] + 268.0642, found 268.0639. 9-(n-Butyl)imidazo[1,2-a]benzimidazole (2g). Eluent: petroleum ether/ethyl acetate (5:1). Yield 52 mg (82%), yellow liquid. 1 H NMR (CDCl 3, 300 MHz) δ 7.48 (d, J = 7.9 Hz, 1H), 7.31 (d, J = 1.7 Hz, 1H), 7.27-7.23 (m, 2H), 7.16-7.09 (m, 2H), 4.15 (t, J = 14.5 Hz, 2H), 1.96-1.83 (m, 2H), 1.47-1.34 (m, 2H), 0.94 (t, J = 14.8 Hz, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 150.2, 136.0, 131.4, 124.6, 123.1, 119.7, 111.0, 109.5, 106.1, 43.2, 30.8, 20.3, 13.8. HRMS (ESI) Calcd for C 13 H 16 N 3 [M+H] + 214.1344, found 214.1330. -S16 -

9-(n-Pentyl)imidazo[1,2-a]benzimidazole (2h). Eluent: petroleum ether/ethyl acetate (5:1). Yield 61 mg (90%), yellow solid. 1 H NMR (CDCl 3, 300 MHz) δ 7.50-7.47 (m, 1H), 7.32 (s, 1H), 7.29-7.23 (m, 2H), 7.18-7.11 (m, 2H), 4.15 (t, J = 14.4 Hz, 2H), 1.96-1.88 (m, 2H), 1.41-1.32 (m, 4H), 0.87 (t, J = 11.0 Hz, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 150.2, 136.0, 131.4, 124.5, 123.1, 120.0, 111.0, 109.5, 106.1, 43.5, 29.1, 28.3, 22.4, 14.0. HRMS (ESI) Calcd for C 14 H 18 N 3 [M+H] + 228.1501, found 228.1497. 9-Phenyl-6-methylimidazo[1,2-a]benzimidazole (2i). Eluent: petroleum ether/ethyl acetate (5:1). Yield 67 mg (90%), white solid, mp 147-149 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.68 (d, J = 8.6 Hz, 2H), 7.47-7.37 (m, 2H), 7.31 (d, J = 8.3 Hz, 1H), 7.25-7.17 (m, 3H), 7.06 (s, 1H), 6.93 (d, J = 8.3 Hz, 1H), 2.34 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 149.0, 136.2, 132.8, 131.3, 131.2, 129.8, 126.5, 125.1, 124.4, 123.3, 111.6, 110.8, 106.2, 21.5. HRMS (ESI) Calcd for C 16 H 14 N 3 [M+H] + 248.1188, found 248.1185. 9-(4-Methyphenyl)-6-methylimidazo[1,2-a]benzimidazole(2j). Eluent: petroleum ether/ethyl acetate (5:1). Yield 71 mg (91%), yellow solid, mp 190-192 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.66 (d, J = 7.6 Hz, 2H), 7.44-7.29 (m, 5H), 7.17 (d, J = 1.7 Hz, -S17 -

1H), 7.06 (d, J = 8.9 Hz, 1H), 2.47 (s, 3H), 2.41 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 149.3, 136.5, 133.5, 133.1, 131.4, 131.0, 130.3, 125.0, 124.3, 123.4, 111.6, 110.7, 106.1, 21.5, 21.2. HRMS (ESI) Calcd for C 17 H 16 N 3 [M+H] + 262.1344, found 262.1344. 9-(3-Methyphenyl)-6-methylimidazo[1,2-a]benzimidazole (2k). Eluent: petroleum ether/ethyl acetate (5:1). Yield 70 mg (90%), yellow liquid. 1 H NMR (CDCl 3, 300 MHz) δ 7.61 (s, 1H), 7.56 (d, J = 6.5 Hz, 1H), 7.47-7.31 (m, 4H), 7.21-7.11 (m, 2H), 7.05 (d, J = 8.3 Hz, 1H), 2.36 (s, 3H), 2.34 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 149.2, 139.9, 136.1, 133.0, 131.4, 131.1, 129.5, 127.4, 125.0, 124.4, 124.0, 120.5, 111.6, 110.9, 106.1, 21.7, 21.5. HRMS (ESI) Calcd for C 17 H 16 N 3 [M+H] + 262.1344, found 262.1341. 9-(3,5-Dimethyphenyl)-6-methylimidazo[1,2-a]benzimidazole (2l). Eluent: petroleum ether/ethyl acetate (5:1). Yield 76 mg (92%), yellow liquid. 1 H NMR (CDCl 3, 300 MHz) δ 7.41-7.36 (m, 3H), 7.35-7.30 (m, 2H), 7.17 (s, 1H), 7.05 (s, 1H), 6.97 (s, 1H), 2.35 (s, 3H), 2.29 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 149.3, 139.5, 135.9, 133.1, 131.4, 131.0, 128.5, 125.0, 124.3, 121.4, 111.5, 111.0, 106.1, 21.6, 21.5. HRMS(ESI) Calcd for C 18 H 18 N 3 [M+H] + 276.1501, found 276.1494. -S18 -

9-(4-Chlorophenyl)-6-methylimidazo[1,2-a]benzimidazole(2m). Eluent: petroleum ether/ethyl acetate (5:1). Yield 78 mg (92%), yellow solid, mp 191-193 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.77 (d, J = 8.3 Hz, 2H), 7.50 (d, J = 8.9 Hz, 2H), 7.50-7.32 (m, 3H), 7.17 (s, 1H), 7.09 (d, J = 8.3 Hz, 1H), 2.49 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 148.8, 134.8, 132.5, 131.8, 131.7, 131.3, 129.9, 125.2, 124.6, 124.4, 111.8, 110.7, 106.4, 21.5. HRMS (ESI) Calcd for C 16 H 13 ClN 3 [M+H] + 282.0798, found 282.0789. 5-Phenybenzimidazo[1,2-a]benzimidazole (2n). Eluent: petroleum ether/ethyl acetate (5:1). Yield 69 mg (81%), yellow solid, mp 136-138 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.81 (d, J = 7.6 Hz, 2H), 7.79-7.73 (m, 2H), 7.70 (d, J = 8.2 Hz, 1H), 7.61-7.57 (m, 2H), 7.48 (d, J = 8.9 Hz, 1H), 7.44-7.40 (m, 1H), 7.35-7.30 (m, 1H), 7.30-7.22 (m, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.6, 147.2, 135.3, 135.0, 130.1, 128.1, 127.5, 125.6, 124.5, 123.3, 123.2, 119.0, 110.9, 110.8, 110.2. HRMS (ESI) Calcd for C 19 H 14 N 3 [M+H] + 284.1188, found 284.1189. -S19 -

5-(4-Methyphenyl)benzimidazo[1,2-a]benzimidazole (2o). Eluent: petroleum ether/ethyl acetate (5:1). Yield 83 mg (93%), yellow solid, mp 146-148 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.72-7.61 (m, 3H), 7.57 (d, J = 8.3 Hz, 2H), 7.40-7.10 (m, 7H), 2.34 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.9, 147.3, 137.7, 135.4, 132.6, 130.6, 128.2, 125.6, 124.6, 123.3, 123.1, 122.0, 120.2, 119.0, 110.8, 110.7, 110.2, 21.3. HRMS (ESI) Calcd for C 20 H 16 N 3 [M+H] + 298.1344, found 298.1339. 5-(3-Methyphenyl)benzimidazo[1,2-a]benzimidazole (2p). Eluent: petroleum ether/ethyl acetate (5:1). Yield 86 mg (96%), yellow solid, mp 140-141 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.70-7.57 (m, 3H), 7.52-7.43 (m, 2H), 7.40-7.30 (m, 2H), 7.26-7.08 (m, 5H), 2.35 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.7, 147.2, 140.2, 135.3, 135.1, 129.9, 128.6, 128.1, 125.6, 125.3, 123.3, 123.2, 122.0, 121.9, 120.3, 119.0, 110.9, 110.7, 110.2, 21.7. HRMS (ESI) Calcd for C 20 H 16 N 3 [M+H] + 298.1344, found 298.1338. 5-(3,5-Dimethyphenyl)benzimidazo[1,2-a]benzimidazole (2q). Eluent: petroleum ether/ethyl acetate (5:1). Yield 91 mg (90%), white solid, mp 179-181 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.73-7.60 (m, 3H), 7.34-7.14 (m, 7H), 6.96 (s, 1H), 2.32 (s, 6H). 13 C NMR (CDCl 3, 75 MHz) δ 152.9, 147.3, 139.9, 135.6, 134.9, 129.7, 128.2, 125.5, 123.3, 123.1, 122.7, 121.9, 120.2, 119.0, 111.0, 110.7, 110.2, 21.5. HRMS (ESI) Calcd for C 21 H 18 N 3 [M+H] + 312.1501, found 312.1495. -S20 -

5-(4-Chlorophenyl)benzimidazo[1,2-a]benzimidazole (2r). Eluent: petroleum ether/ethyl acetate (5:1). Yield 78 mg (82%), white solid, mp 172-174 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.85-7.72 (m, 5H), 7.56 (d, J = 8.6 Hz, 2H), 7.47 (d, J = 7.2 Hz, 1H), 7.39-7.23 (m, 4H). 13 C NMR (CDCl 3, 75 MHz) δ 152.3, 147.0, 134.8, 133.9, 133.0, 130.2, 128.1, 125.7, 123.4, 123.3, 122.5, 120.6, 119.1, 110.9, 110.7, 110.3. HRMS (ESI) Calcd for C 19 H 13 ClN 3 [M+H] + 318.0798, found 318.0788. 5-Phenyl-8,9-dimethylbenzimidazo)[1,2-a]benzimidazole (2s). Eluent: petroleum ether/ethyl acetate (5:1). Yield 84 mg (90%), white solid, mp 185-187 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.80 (d, J = 7.6 Hz, 2H), 7.71-7.64 (m, 1H), 7.61-7.35 (m, 6H), 7.30-7.18 (m, 2H), 2.41 (s, 3H), 2.36 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.2, 145.5, 135.5, 135.0, 131.7, 130.0, 129.0, 127.4, 126.4, 125.7, 124.5, 123.0, 122.0, 119.5, 110.8, 110.7, 110.6, 20.6, 20.4. HRMS (ESI) Calcd for C 21 H 18 N 3 [M+H] + 312.1501, found 312.1490. -S21 -

5-(4-Methyphenyl)-8,9-dimethylbenzimidazo)[1,2-a]benzimidazole (2t). Eluent: petroleum ether/ethyl acetate (5:1). Yield 89 mg (91%), white solid, mp 195-197 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.57-7.44 (m, 3H), 7.36 (s, 1H), 7.31 (s, 1H), 7.28-7.19 (m, 3H), 7.11-6.99 (m, 2H), 2.29 (s, 3H), 2.25 (s, 3H), 2.21 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.4, 145.6, 137.3, 135.1, 132.8, 131.5, 130.5, 128.8, 126.4, 125.6, 124.4, 122.8, 121.7, 119.4, 110.7, 110.6, 110.5, 21.3, 20.6, 20.4. HRMS (ESI) Calcd for C 22 H 20 N 3 [M+H] + 326.1657, found 326.1657. 5-(3-Methyphenyl)-8,9-dimethybenzimidazo)[1,2-a]benzimidazole (2u). Eluent: petroleum ether/ethyl acetate (5:1). Yield 91 mg (93%), yellow solid, mp 148-150 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.74-7.69 (m, 1H), 7.66-7.56 (m, 2H), 7.54 (s, 2H), 7.51-7.43 (m, 2H), 7.33-7.20 (m, 3H), 2.37 (s, 3H), 2.32 (s, 3H), 2.28 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.4, 145.5, 140.1, 135.3, 135.2, 131.6, 129.8, 128.9, 128.4, 126.5, 125.7, 125.2, 122.9, 121.8, 119.5, 110.7, 110.5, 21.7, 20.6, 20.4. HRMS (ESI) Calcd for C 22 H 20 N 3 [M+H] + 326.1657, found 326.1647. -S22 -

5-(3,5-Dimethyphenyl)-8,9-dimethylbenzimidazo)[1,2-a]benzimidazole (2r). Eluent: petroleum ether/ethyl acetate (5:1). Yield 99 mg (97%), white solid, mp 216-217 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.54-7.46 (m, 1H), 7.38 (s, 1H), 7.34 (s, 1H), 7.30-7.22 (m, 3H), 7.12-7.01 (m, 2H), 6.89 (s, 1H), 2.30-2.21 (m, 12H). 13 C NMR (CDCl 3, 75 MHz) δ 152.4, 145.6, 139.8, 135.4, 135.2, 131.5, 129.4, 128.8, 126.4, 125.6, 122.8, 122.5, 121.7, 119.4, 110.8, 110.4, 21.6, 20.6, 20.4. HRMS (ESI) Calcd for C 23 H 22 N 3 [M+H] + 340.1814, found 340.1801. 5-(4-Chlorophenyl)-8,9-dimethylbenzimidazo)[1,2-a]benzimidazole (2w). Eluent: petroleum ether/ethyl acetate (5:1). Yield 98 mg (95%), white solid, mp 217-219 o C. 1 H NMR (CDCl 3, 300 MHz) δ 7.78 (d, J = 8.3 Hz, 2H), 7.72 (d, J = 8.1 Hz, 1H), 7.60-7.44 (m, 5H), 7.35-7.22 (m, 2H), 2.34 (s, 3H), 2.29 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.0, 145.3, 134.7, 134.1, 132.8, 131.9, 130.1, 129.3, 126.4, 125.8, 125.6, 123.1, 122.2, 119.5, 110.8, 110.7, 110.6, 20.5, 20.4. HRMS (ESI) Calcd for C 21 H 17 ClN 3 [M+H] + 346.1111, found 346.1097. -S23 -

5-(2-Nitrophenyl)-8,9-dimethylbenzimidazo)[1,2-a]benzimidazole (2x). Eluent: petroleum ether/ethyl acetate (3:1). Yield 99 mg (92%), yellow solid, mp 247-248 o C. 1 H NMR (CDCl 3, 300 MHz) δ 8.22 (d, J = 4.9 Hz, 1H), 7.90-7.76 (m, 3H), 7.73-7.61 (m, 2H), 7.56 (s, 1H), 7.37-7.22 (m, 2H), 6.90 (s, 1H), 2.40 (s, 3H), 2.38 (s, 3H). 13 C NMR (CDCl 3, 75 MHz) δ 152.3 146.9, 145.6, 134.9, 133.3, 132.3, 131.6, 130.2, 129.6, 128.4, 126.7, 124.1, 123.0, 120.5, 119.1, 112.1, 110.9, 110.3, 20.4, 20.2. HRMS (ESI) Calcd for C 21 H 17 N 4 O 2 [M+H] + 357.1352, found 357.1351. Crystal preparation and X-ray diffraction analysis of compound 2m Crystal preparation of compound 2m. Compound 2m (20.0 mg) was dissolved in CH 2 Cl 2 (1 ml), and it was crystallized to give crystal as yellow prisms after the solvent was slowly volatilized in 12 h at room temperature (~ 20 C). X-ray diffraction analysis of compound 2m The room temperature (295±2 K) single-crystal X-ray experiments were performed on a Rigaku Raxis-Rapid diffractometer equipped with graphite monochromatized Mo K α radiation. Unit cell was obtained and refined by 8907 reflections with 3.0 < θ < 27.5. No decay was observed except the statistic fluctuation in the data collection. Raw intensities were corrected for Lorentz and polarization effects. Direct phase determination yielded the positions of all non-hydrogen atoms. All non-hydrogen atoms were subjected to anisotropic refinement. All hydrogen atoms were generated geometrically with C-H bonds of 0.93-0.96 Å according to criteria described in the SHELXTL manual (Bruker, 1997). 5 They were included in the refinement with U iso (H) = 1.2U eq (for C) and 1.5 U eq (for methyl). The final full-matric least-square refinement on F 2 converged with R 1 = 0.0410 and wr 2 = 0.0850 for 2459 observed reflections [I 2σ(I)]. The final difference electron density map shows no features. Details of -S24 -

crystal parameters, data collection and structure refinement are given in Table 1. Data collection was controlled by CrystalClear program (Rigaku Inc., 2004). Computations were performed using the SHELXTL NT ver. 5.10 program package (Bruker, 1997) on an IBM PC computer. Analytic expressions of atomic scattering factors were employed, and anomalous dispersion corrections were incorporated (International Tables for X-ray Crystallography, 1989). 6 Crystal drawings were produced with XP (Bruker, 1998). Table 1. Details of Data Collection, Processing and Structure Refinement Sample code WangXQ-1 Molecular formula C 16 H 12 N 3 Cl Molecular weight 281.74 Color and habit yellow prism Crystal size 0.10 0.12 0.16 mm Crystal system monoclinic Space group P2 1 /c (No. 14) Unit cell parameters a = 8.5445(6) Å α = 90.00 b = 13.2014(10) Å β = 102.815(2) c = 12.4279(11) Å γ = 90.00 V = 1366.95(18) Å 3 Z = 4 F(000) = 584 Density (calcd) 1.369 g/cm 3 Diffractometer Rigaku Raxis-Rapid Radiation graphite-monochromatized Mo K α, λ = 0.71073 Å Temperature 295±2K Scan type ω-scan Data collection range -10 < h < 11, -17 < k < 15, -16 < l < 16; θ max = 27.5 Reflections measured Total: 13113 Unique (n): 3112 Observed [I 2σ(I)]: 2549 Absorption coefficient 0.272 mm -1 No. of variables, p 181 1 Weighting scheme w = 2 2 2 σ ( F ) + (0.001 P) + 0.8P o P = (F o 2 + 2F c 2 )/3 Σ Fo Fc R1 = (for all reflections) 0.0490 0.0410 (for observed data) Σ F o -S25 -

wr2 = 2 2 2 Σ[ wf ( o Fc ) ] 2 2 ΣwF ( ) (for all reflections) 0.0879 0.0850 (for observed data) o Goof = S = Σ[ wf ( 2 F 2 ) 2 ] o c n-p 1.031 Largest and mean Δ/σ 0.000, 0.000 Residual extrema in final difference map -0.333 to 0.247 e Å -3 Table 2. Atomic coordinates and equivalent isotropic temperature factors* (Å 2 ) Atoms x y z U eq. Cl(1) 0.98629(7) 1.03273(4) 0.66016(5) 0.07116(18) N(1) 0.68750(16) 0.62852(9) 0.65509(11) 0.0394(3) N(2) 0.54526(18) 0.63676(11) 0.81042(12) 0.0483(3) N(3) 0.57640(15) 0.49415(10) 0.71801(11) 0.0412(3) C(1) 0.60496(18) 0.59538(12) 0.73266(13) 0.0391(3) C(2) 0.4710(2) 0.55370(16) 0.84846(16) 0.0565(5) C(3) 0.4870(2) 0.46698(15) 0.79426(15) 0.0522(4) C(4) 0.64036(18) 0.45880(12) 0.63058(13) 0.0403(4) C(5) 0.6462(2) 0.36365(13) 0.58587(15) 0.0480(4) C(6) 0.7206(2) 0.35330(14) 0.49765(16) 0.0520(4) C(7) 0.7874(2) 0.43806(14) 0.45806(15) 0.0528(4) C(8) 0.7841(2) 0.53392(13) 0.50407(14) 0.0478(4) C(9) 0.70950(18) 0.54377(11) 0.59126(13) 0.0386(3) C(10) 0.7310(3) 0.25038(16) 0.4447(2) 0.0763(7) C(11) 0.76058(18) 0.72552(11) 0.65571(13) 0.0361(3) C(12) 0.74212(19) 0.78036(12) 0.55881(13) 0.0416(4) C(13) 0.8135(2) 0.87465(13) 0.55964(14) 0.0450(4) C(14) 0.90220(19) 0.91249(12) 0.65787(14) 0.0427(4) C(15) 0.92127(19) 0.85900(12) 0.75500(14) 0.0430(4) C(16) 0.84931(19) 0.76503(12) 0.75420(13) 0.0404(4) *U eq. defined as one third of the trace of the orthogonalized U tensor. Table 3. Bond lengths (Å) and bond angles ( o ) Cl(1)-C(14) 1.7401(16) C(5)-C(6) 1.391(3) N(1)-C(1) 1.3856(19) C(6)-C(7) 1.394(3) N(1)-C(9) 1.4080(19) C(6)-C(10) 1.521(3) N(1)-C(11) 1.4239(19) C(7)-C(8) 1.392(2) N(2)-C(1) 1.308(2) C(8)-C(9) 1.380(2) N(2)-C(2) 1.400(2) C(11)-C(12) 1.384(2) -S26 -

N(3)-C(1) 1.363(2) C(11)-C(16) 1.390(2) N(3)-C(3) 1.390(2) C(12)-C(13) 1.385(2) N(3)-C(4) 1.400(2) C(13)-C(14) 1.380(2) C(2)-C(3) 1.350(3) C(14)-C(15) 1.377(2) C(4)-C(5) 1.379(2) C(15)-C(16) 1.384(2) C(4)-C(9) 1.405(2) C(1)-N(1)-C(9) 107.05(12) C(5)-C(6)-C(10) 120.63(18) C(1)-N(1)-C(11) 124.78(13) C(7)-C(6)-C(10) 119.78(18) C(9)-N(1)-C(11) 127.20(13) C(8)-C(7)-C(6) 122.54(17) C(1)-N(2)-C(2) 101.67(15) C(9)-C(8)-C(7) 117.59(16) C(1)-N(3)-C(3) 105.73(14) C(8)-C(9)-C(4) 120.07(15) C(1)-N(3)-C(4) 109.95(13) C(8)-C(9)-N(1) 131.29(15) C(3)-N(3)-C(4) 144.22(15) C(4)-C(9)-N(1) 108.63(14) N(2)-C(1)-N(3) 114.86(14) C(12)-C(11)-C(16) 120.30(14) N(2)-C(1)-N(1) 136.40(15) C(12)-C(11)-N(1) 120.03(14) N(3)-C(1)-N(1) 108.68(14) C(16)-C(11)-N(1) 119.67(14) C(3)-C(2)-N(2) 113.10(16) C(11)-C(12)-C(13) 119.90(15) C(2)-C(3)-N(3) 104.63(15) C(14)-C(13)-C(12) 119.11(15) C(5)-C(4)-N(3) 132.19(15) C(15)-C(14)-C(13) 121.67(15) C(5)-C(4)-C(9) 122.11(16) C(15)-C(14)-Cl(1) 119.05(13) N(3)-C(4)-C(9) 105.69(13) C(13)-C(14)-Cl(1) 119.24(13) C(4)-C(5)-C(6) 118.09(16) C(14)-C(15)-C(16) 119.19(15) C(5)-C(6)-C(7) 119.58(16) C(15)-C(16)-C(11) 119.82(15) Table 4. Anisotropic thermal parameters* (Å 2 ) Atoms U 11 U 22 U 33 U 23 U 13 U 12 Cl(1) 0.0813(4) 0.0538(3) 0.0750(4) 0.0039(2) 0.0099(3) -0.0339(3) N(1) 0.0470(7) 0.0329(7) 0.0394(7) 0.0001(6) 0.0120(6) -0.0056(6) N(2) 0.0534(8) 0.0503(8) 0.0432(8) -0.0001(7) 0.0150(6) -0.0035(7) N(3) 0.0396(7) 0.0375(7) 0.0455(8) 0.0043(6) 0.0071(6) -0.0054(6) C(1) 0.0395(8) 0.0368(8) 0.0389(8) 0.0037(7) 0.0044(6) -0.0035(6) C(2) 0.0577(11) 0.0663(12) 0.0497(10) 0.0062(9) 0.0208(9) -0.0079(9) C(3) 0.0500(10) 0.0541(11) 0.0539(11) 0.0139(9) 0.0142(8) -0.0106(8) C(4) 0.0358(8) 0.0373(8) 0.0443(9) 0.0016(7) 0.0012(6) -0.0029(6) C(5) 0.0437(9) 0.0359(8) 0.0592(11) -0.0007(8) 0.0000(8) -0.0044(7) C(6) 0.0476(10) 0.0433(10) 0.0583(11) -0.0111(8) -0.0029(8) 0.0029(8) C(7) 0.0538(11) 0.0550(11) 0.0488(10) -0.0097(8) 0.0099(8) 0.0037(8) C(8) 0.0519(10) 0.0454(9) 0.0473(10) -0.0022(8) 0.0133(8) -0.0040(8) C(9) 0.0384(8) 0.0348(8) 0.0401(8) -0.0009(7) 0.0037(6) -0.0022(6) C(10) 0.0858(16) 0.0518(12) 0.0871(17) -0.0234(11) 0.0098(13) 0.0047(11) C(11) 0.0372(8) 0.0316(7) 0.0400(8) 0.0002(6) 0.0096(6) -0.0012(6) C(12) 0.0454(9) 0.0425(9) 0.0355(8) -0.0005(7) 0.0058(7) -0.0077(7) -S27 -

C(13) 0.0500(9) 0.0453(9) 0.0399(9) 0.0083(7) 0.0106(7) -0.0082(7) C(14) 0.0402(8) 0.0366(8) 0.0519(10) -0.0002(7) 0.0117(7) -0.0090(7) C(15) 0.0431(9) 0.0417(9) 0.0414(9) -0.0047(7) 0.0031(7) -0.0038(7) C(16) 0.0467(9) 0.0364(8) 0.0365(8) 0.0036(7) 0.0057(7) 0.0020(7) *The exponent takes the form: -2π 2 ΣΣU ij h i h j a * * i a j Table 5. Coordinates and isotropic temperature factors* (Å 2 ) for H atoms Atoms x y z U eq. H(2A) 0.4164 0.5578 0.9052 0.068 H(3A) 0.4470 0.4033 0.8055 0.063 H(5A) 0.6017 0.3080 0.6139 0.058 H(7A) 0.8359 0.4302 0.3986 0.063 H(8A) 0.8306 0.5893 0.4770 0.057 H(10A) 0.7711 0.2586 0.3790 0.115 H(10B) 0.6262 0.2202 0.4262 0.115 H(10C) 0.8021 0.2073 0.4955 0.115 H(12A) 0.6819 0.7539 0.4932 0.050 H(13A) 0.8017 0.9120 0.4949 0.054 H(15A) 0.9818 0.8857 0.8203 0.052 H(16A) 0.8602 0.7284 0.8194 0.048 *The exponent takes the form: -8π 2 Usin 2 θ/λ 2 ORTEP drawing of C 16 H 12 N 3 Cl (2m) with 35% probability ellipsoids, showing the atomic numbering scheme. -S28 -

c a b A packing view along the b direction References (1) Sreedhar, B.; Arundhathi, R.; Linga Reddy, P.; Kantam, M. L. J. Org. Chem. 2009, 74, 7951-7954. (2) A. J. Blake, B. A. J. Clark, H. McNab, C. C. Sommerville, J. Chem. Soc. Perkin Trans. 1 1997, 1605-1608. (3) Tajbakhsh, M.; Hosseinzadeh, R.; Alinezhad, H.; Ghahari, S.; Heydar, A.; Khaksar, S. Synthesis 2011, 490-496. (4) Altman, R. A.; Anderson, K. W.; Buchwald, S. L. J. Org. Chem. 2008, 73, 5167 5169. (5) Bruker. SHELXTL. Structure Determination Programs, Version 5.10, Bruker AXS Inc., 6300 Enterprise Lane, Madison, WI 53719-1173, USA, 1997. (6) International Tables for X-ray Crystallography: Vol. C (Kluwer Academic Publishers, Dordrecht) Tables 4.2.6.8 and 6.1.1.4, 1989. -S29 -

N N NH 1a -S30 -

N NH N 1a -S31 -

-S32-1b

-S33-1b

N NH N 1c -S34 -

N NH N 1c -S35 -

N NH N 1d -S36 -

N N NH 1d -S37 -

-S38-1e

-S39-1e

-S40-1f

-S41-1f

-S42-1g

-S43-1g

-S44-1h

-S45-1h

-S46-1i

-S47-1i

-S48-1j

-S49-1j

-S50-1k

-S51-1k

-S52-1l

-S53-1l

-S54-1m

-S55-1m

-S56-1n

-S57-1n

-S58-1o

-S59-1o

-S60-1p

-S61-1p

-S62-1q

-S63-1q

-S64-1r

-S65-1r

-S66-1s

-S67-1s

-S68-1t

-S69-1t

-S70-1u

-S71-1u

-S72-1v

-S73-1v

-S74-1w

-S75-1w

-S76-1x

-S77-1x

-S78-2a

-S79-2a

-S80-2b

-S81-2b

-S82-2c

-S83-2c

-S84-2d

-S85-2d

-S86-2e

-S87-2e

-S88-2f

-S89-2f

-S90-2g

-S91-2g

-S92-2h

-S93-2h

N N N 2i -S94 -

N N N 2i -S95 -

-S96-2j

-S97-2j

N N N 2k -S98 -

N N N 2k -S99 -

N N N 2l -S100 -

N N N 2l -S101 -

-S102-2m

-S103-2m

-S104-2n

-S105-2n

-S106-2o

-S107-2o

-S108-2p

-S109-2p

-S110-2q

-S111-2q

-S112-2r

-S113-2r

-S114-2s

-S115-2s

-S116-2t

-S117-2t

-S118-2u

-S119-2u

-S120-2v

-S121-2v

-S122-2w

-S123-2w

-S124-2x

-S125-2x