p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of

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1 Supporting Information for: p-toluenesulfonic Acid-Mediated 1,3-Dipolar Cycloaddition of Nitroolefins with NaN 3 for Synthesis of 4-Aryl-NH-1,2,3-triazoles Xue-Jing Quan, Zhi-Hui Ren, Yao-Yu Wang, and Zheng-Hui Guan* Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi an , P. R. China guanzhh@nwu.edu.cn CONTENTS 1. General information S2 2. Typical procedure for preparation of nitroolefins S2 3. Representative procedure for synthesis of 4-aryl-NH-1,2,3-triazoles S3 4. Characterization data of products s3-s8 5. Copies of 1 H and 13 C NMR spectras s9-s54 - S 1 -

2 1. General information 1 H and 13 CNMR spectra were recorded on Varian instrument (400 MHz) and (100 MHz). The following abbreviations (or combinations thereof) were used to explain multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, b = broad. Coupling constants, J were reported in Hertz unit (Hz). Preparative TLC was performed on TLC plates. Analytical thin layer chromatography was performed on 10-25um silica gel GF-254, visualization was carried out with UV light. Flash column chromatography was performed with SiO 2 ( mesh). Unless otherwise stated, all reagents and solvents were purchased from commercial suppliers and used without further purification. 2. Typical procedure for preparation of nitroolefins 1-3 Benzaldehyde (10.0 mmol), nitromethane (12.0 mmol) and ammonium acetate (6.0 mmol) were added to 7 ml of glacial acetic acid. The resulting solution was refluxed for 2 h. Then the reaction mixture was poured into ice-water, and the yellow solid thus formed was collected by filtration to give crude product. The solid residue was purified by flash column chromatography (ethyl acetate and hexanes as eluent). The desired nitroolefin was obtained in 70% yield. Other Nitroolefins were prepared by the same procedure. References: (1) Yan, M.-C.; Jang, Y.-J.; Yao, C.-F. Tetrahedron Lett. 2001, 42, (2) Gairaud, C. B.; Lappin, G. R. J. Org. Chem. 1953, 18, 1 (3) Ganesh, M.; Namboothiri, I. N. N. Tetrahedron, 2007, 63, S 2 -

3 3. Representative procedure for synthesis of 4- aryl -NH-1,2,3-triazoles CAUTION: all the experiments were performed in a well-ventilated fume hood and behind a blast shield. Nitroolefin 1a (0.3 mmol) and NaN 3 (0.45 mmol) were stirred in DMF (3 ml), then, p-tsoh (0.15 mmol) was carefully added to the mixture. The mixture was stirred at 60 o C in air for 1h. After completion of the reaction (detected by TLC), the reaction mixture was cooled to room temperature, quenched with H 2 O (10 ml) and extracted with EtOAc (3 10 ml). The organic layers was dried over anhydrous Na 2 SO 4 and evaporated in vacuo. The residue was purified by flash column chromatography on silica gel (SiO 2, hexanes/etoac) to afford the 4-phenyl-NH-1,2,3-triazole 2a as white solid in 93% yield. Other of 4-aryl-NH-1,2,3-triazoles were prepared by the similar procedure. 4. Characterization data of products 2a: Yield: 93% (40.4 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA : δ (s, 1 H), 8.35 (s, 1 H), 7.87 (d, J = 6.8 Hz, 2 H), 7.44 (d, J = 7.2 Hz, 2 H), 7.35 (d, J = 6.8 Hz, 1 H); 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 145.3, 130.4, 129.0, 128.2, 127.4, HRMS Calcd (ESI) m/z for C 8 H 8 N 3 : [M+H] , found: b: Yield: 94% (44.8 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.27 (s, 1 H), 7.75 (d, J = 6.8 Hz 2 H), 7.24 (d, J = 6.4 Hz, 2 H), 2.30 (s, 3 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 145.1, 137.6, 129.5, 127.5, 125.6, HRMS Calcd (ESI) m/z for C 9 H 10 N 3 : [M+H] , found: S 3 -

4 2c: Yield: 94% (44.8 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.10 (s, 1 H), 7.48 (d, J = 13.6 Hz 2 H), 7.11 (s, 1 H), 6.94 (s, 1 H), 2.13 (s, 3 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 145.4, 138.3, 130.3, 129.0, 127.5, 126.3, 122.9, 104.8, HRMS Calcd (ESI) m/z for C 9 H 10 N 3 : [M+H] , found: d: Yield: 97% (50.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.22 (s, 1 H), 7.79 (d, J = 8.4 Hz, 2 H), 7.01 (d, J = 8.8 Hz, 2 H), 3.77 (s, 3 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 159.4, 144.9, 127.1, 122.8, 114.4, HRMS Calcd (ESI) m/z for C 9 H 10 N 3 O: [M+H] , found: e: Yield: 95% (49.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.22 (s, 1 H), 8.01 (d, J = 7.2 Hz, 1 H), 7.33 (t, J = 6.8 Hz, 1 H), 7.11 (d, J = 8.4 Hz, 1 H), 7.04 (t, J = 7.2 Hz, 1 H), 3.89 (s, 3 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 155.9, 129.3, 127.4, 120.7, 118.5, 111.7, HRMS Calcd (ESI) m/z for C 9 H 10 N 3 O: [M+H] , found: f: Yield: 73% (35.3 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ (s, 1 H), 8.30 (s, 1 H), 7.90 (d, J = 6.8 Hz, 1 H), 7.17 (d, J = 6.8 Hz, 1 H), 7.00 (d, J = 7.6 Hz, 1 H), 6.90 (t, J = 6.0 Hz, 1 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 154.5, 141.9, 129.2, 127.3, 119.5, 116.4, HRMS Calcd (ESI) m/z for C 8 H 8 N 3 O: [M+H] , found: g: Yield: 96% (46.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.32 (s, 1 H), 7.90 (s, 2 H), 7.25(t, J = 8.4 Hz, 2 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 163.2, 160.8, 144.6, (d, J CF =8.1 Hz), 127.0, (d, J CF =21.6 Hz). HRMS Calcd (ESI) m/z for C 8 H 7 N 3 F: [M+H] , found: S 4 -

5 2h: Yield: 84% (45.1 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.39 (s, 1 H), 7.88 (d, J = 6.8 Hz, 2 H), 7.50 (d, J = 7.2 Hz, 2 H). 13 C NMR (DMSO-d 6, 100 MHz) 1 drop TFA: δ 144.5, 132.7, 129.4, 129.1, HRMS Calcd (ESI) m/z for C 8 H 7 N 3 Cl: [M+H] , found: i: Yield: 93% (49.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ (s, 1H), 8.35 (s, 1H), 7.92 (d, J = 6.4 Hz, 1 H), 7.54 (d, J = 7.2 Hz, 1 H), (m, 2 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 142.4, 131.0, 130.3, 130.3, 129.7, 129.3, HRMS Calcd (ESI) m/z for C 8 H 7 N 3 Cl: [M+H] , found: Cl N N NH Cl 2j 2j: Yield: 90% (57.5 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.41 (s, 1 H), 7.96 (d, J = 8.0 Hz, 1 H), 7.72 (s, 1 H), 7.52 (d, J = 8.4 Hz, 1 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 141.6, 133.3, 131.7, 131.2, 129.7, 128.4, HRMS Calcd (ESI) m/z for C 8 H 6 N 3 Cl 2 : [M+H] , found: k: Yield: 66% (44.2 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.38 (s, 1 H), 7.82 (d, J = 8.4 Hz, 2 H), 7.63 (d, J = 8.4 Hz, 2 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 144.5, 131.9, 129.8, 127.6, HRMS Calcd (ESI) m/z for C 8 H 7 N 3 Br: [M+H] , found: l: Yield: 70% (39.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.57 (s, 1 H), 8.52 (s, 1 H), 8.23 (d, J = 6.8 Hz, 1 H), 8.09 (d, J = 7.6 Hz, 1 H), 7.65 (t, J = 7.6 Hz, 1 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 148.3, 143.8, 132.3, 131.7, 130.5, 127.3, 122.5, HRMS Calcd (ESI) m/z for C 8 H 7 N 4 O 2 : [M+H] , found: S 5 -

6 2m: Yield: 66% (33.7 mg), Yellow solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.54 (s, 1 H), 8.05 (d, J = 8.0 Hz, 2 H), 7.88 (d, J = 8.0 Hz, 2 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 144.2, 135.2, 133.1, 126.2, 118.9, HRMS Calcd (ESI) m/z for C 9 H 7 N 4 : [M+H] , found: N N NH MeOOC 2n 2n: Yield: 71% (43.0 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz): δ 8.53 (s, 1H), 8.05 (s, 4H), 3.89 (s, 3H). 13 C NMR (DMSO-d 6, 100 MHz): δ 166.0, 135.1, 129.9, 128.9, 125.6, HRMS Calcd (ESI) m/z for C 10 H 10 N 3 O 2 : [M+H] , found: o: Yield: 85% (34.4 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.16 (s, 1 H), 7.76 (s, 1 H), 6.83 (s,1 H), 6.60(s, 1 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 145.8, 143.0, 138.0, 126.8, 111.7, HRMS Calcd (ESI) m/z for C 6 H 5 N 3 NaO: [M+Na] , found: p: Yield: 87% (39.4 mg), brown solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.24 (s, 1 H), 7.54 (d, J = 4.4 Hz, 1 H), 7.50 (d, J = 2.4 Hz, 1 H), 7.13 (d, J = 4.0 Hz, 1 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 141.1, 132.8, 128.0, 126.9, 125.8, HRMS Calcd (ESI) m/z for C 6 H 6 N 3 S: [M+H] , found: q: Yield: 85% (46.9 mg), Yellow solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 11.45(s, 1 H), 8.19 (s, 1 H), 8.08 (d, J = 7.2 Hz, 1 H), 7.88 (s, 1 H), 7.47 (d, J = 7.6 Hz, 1 H), (m, 2 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 136.5, 124.8, 123.9, 121.9, 120.1, 119.8, HRMS Calcd (ESI) m/z for C 10 H 9 N 4 : [M+H] , found: S 6 -

7 2r: Yield: 74% (38.0 mg), Yellow solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 8.09 (s, 1 H), 7.57(s, 2 H), (m, 5 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 143.8, 136.6, 130.8, 128.9, 128.1, 126.5, HRMS Calcd (ESI) m/z for C 10 H 10 N 3 : [M+H] , found: N N NH 2s 2s: Yield: 94% (44.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 9.02 (d, J = 7.2 Hz, 2 H), 8.77 (t, J = 6.8 Hz, 2 H), 8.67 (d, J = 6.8 Hz, 1 H), 3.75 (s, 3 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 141.7, 131.1, 128.8, 127.6, 126.7, HRMS Calcd (ESI) m/z for C 9 H 10 N 3 : [M+H] , found: t: Yield: 98% (50.9 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 7.66 (d, J = 7.2 Hz, 2 H), 7.45 (t, J = 6.8 Hz, 2 H), 7.35 (t, J=7.2 Hz, 1 H), (m, 2 H), 1.22 (t, J=7.2 Hz, 3 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 141.3, 131.2, 128.9, 127.8, 126.9, 18.0, HRMS Calcd (ESI) m/z for C 10 H 12 N 3 : [M+H] , found: u: Yield: 95% (63.0 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 7.51 (d, J = 6.4 Hz, 4 H), 7.37 (d, J = 7.2 Hz, 6 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 141.0, 130.6, 128.8, 128.4, HRMS Calcd (ESI) m/z for C 14 H 12 N 3 : [M+H] , found: v: Yield: 95% (71.0 mg), White solid. 1 H NMR (DMSO-d 6, 400 MHz), 1 drop TFA: δ 7.71 (d, J = 5.6 Hz, 1 H), 7.36 (t, J = 8.0 Hz, 5 H), 7.05 (s, 2 H), 6.77 (s, 1 H). 13 C NMR (DMSO-d 6, 100 MHz), 1 drop TFA: δ 152.6, 140.6, 139.2, 136.3, 130.1, 128.7, 127.1, 122.7, 122.3, 117.5, 116.0, HRMS Calcd (ESI) m/z for C 15 H 12 N 3 O: [M+H] , found: S 7 -

8 4a: Yield: 60% (42.3 mg), White solid. 1 H NMR (CDCl 3, 400 MHz): δ 7.65 (s, 1H), 7.34 (s, 3H), 7.18 (s, 5H), 6.99(s, 2H), 5.46 (s, 2H). 13 C NMR (CDCl 3, 100 MHz): δ 138.1, 135.4, 133.2, 129.4, 128.8, 128.8, 128.7, 128.0, 127.0, 126.8, HRMS Calcd (ESI) m/z for C 15 H 14 N 3 : [M+H] , found: S 8 -

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