Supporting Information for. Copper-Catalyzed Radical Reaction of N-Tosylhydrazones: Stereoselective Synthesis of (E)-Vinyl Sulfones

Supporting Information for Copper-Catalyzed Radical Reaction of N-Tosylhydrazones: Stereoselective Synthesis of (E)-Vinyl Sulfones Shuai Mao, Ya-Ru Gao, Xue-Qing Zhu, Dong-Dong Guo, Yong-Qiang Wang* Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of Ministry of Education, Department of Chemistry & Materials Science, Northwest University, Xi an 710069, P.R. China. E-mail: wangyq@nwu.edu.cn Table of content 1. General information S1 2. Tosylhydrazones employed for transformations S2 3. General procedure A (synthesis of vinyl sulfones) S4 4. General procedure B (synthesis of alkynes from N-tosylhydrazones) S5 5. General procedure C (the reaction mechanism) S6 6. Compound characterization S7-S21 7. References S22 8. Spectral data S23-S60

1. General Information: All reactions were carried out under argon. Unless otherwise noted, All reagents and solvents were obtained from commercial suppliers and used without further purification. The progress of the reactions was monitored by TLC with silica gel plates (GF254), and the visualization was carried out under UV light. The 1 H and the 13 C NMR spectroscopic data were recorded with a Varian Unity Inova-400 spectrometer ( 1 H and 13 C NMR at 400 and 100 MHz, respectively). CDCl 3 was used as the NMR solvent, unless otherwise noted. Infrared (IR) data were recorded as films on potassium bromide plates with a Bruker Tensor 27 FT-IR spectrometer. Absorbance frequencies are reported in reciprocal centimeters (cm 1 ). High resolution mass spectra were acquired with a Bruker Daltonics MicroTof-Q II mass spectrometer. X-ray crystal structure analyses were measured on a Bruker Smart APEXIICCD instrument using Mo-Kα radiation. The structures were solved and refined by using the SHELXTL software package. S1

2. Tosylhydrazones employed for the transformation: 2.1 Typical reaction procedure for the synthesis of N-tosylhydrazones 1 When the carbonyl compound is solid: A mixture of carbonyl compound (5 mmol) and tosylhydrazide (5 mmol) in MeOH (7.5 ml) were heated at 70 o C for 0.5-3 h to obtain the corresponding N-tosylhydrazone as white precipitate, which was filtered and washed with petroleum ether (5 ml 3) and dried under vacuum to obtain pure compound. When the carbonyl compound is liquid: Carbonyl compound (5 mmol) was added to a solution of tosylhydrazide (5 mmol) in MeOH (7.5 ml) at room temperature and the solution was heated at 70 o C for 0.5-3 h to obtain the corresponding N-tosylhydrazone as white precipitate, which was filtered and washed with petroleum ether (5 ml 3) and dried under vacuum to obtain pure compound. S2

3. General procedure A (Synthesis of vinyl sulfones) (2a-2z ): Table 1. Optimization of the Reaction Conditions a Me O S O N NH copper catalyst solvent atm (1 atm) temp, time O S O 1a Me 2a entry catalyst (mol %) temp ( C) solvent Atm (1 atm) time (h) yield (%) b 1 Cu(OAc) 2 H 2 O (20) 90 xylene air 6 34 2 c Cu(OAc) 2 H 2 O (20) 90 xylene O 2 6 trace 3 Cu(OAc) 2 H 2 O (20) 90 xylene Ar 4 92 4 Cu(OAc) 2 H 2 O (20) 80 xylene Ar 25 23 5 Cu(OAc) 2 H 2 O (20) 120 xylene Ar 2 92 6 Cu(OAc) 2 H 2 O (20) 140 xylene Ar 1.5 91 7 Cu(OAc) 2 (20) 90 xylene Ar 4 30 8 d Cu(OAc) 2 (20) 90 xylene Ar 4 65 9 [(CH 3 CN) 4 Cu]PF 6 (20) 90 xylene Ar 6 16 10 CuBr 2 (20) 90 xylene Ar 6 0 11 CuCl (20) 90 xylene Ar 6 0 12 CuOAc (20) 90 xylene Ar 6 23 13 Cu 2 O (20) 90 xylene Ar 6 24 14 CuBr (20) 90 xylene Ar 6 0 15 Cu(OAc) 2 H 2 O (20) 110 toluene Ar 4 36 16 Cu(OAc) 2 H 2 O (20) 110 DMF Ar 4 19 17 Cu(OAc) 2 H 2 O (20) 140 DMSO Ar 4 22 18 Cu(OAc) 2 H 2 O (20) 80 CH 3 CN Ar 4 0 19 Cu(OAc) 2 H 2 O (20) 100 1,4-dioxane Ar 4 10 20 Cu(OAc) 2 H 2 O (20) 84 1,2-dichlorethane Ar 4 tace 21 Cu(OAc) 2 H 2 O (15) 90 xylene Ar 6 93 22 Cu(OAc) 2 H 2 O (10) 90 xylene Ar 10 65 23-90 xylene Ar 10 0 a Reaction conditions: 1a (1 mmol), catalyst (20 mol %) in solvent (3 ml) at the specified temperature. b Isolated yields after filtration through a short pad of aluminum oxide. c Getting the 2-phenylacetophenone (43% isolated yield) and Benzil (33% isolated yield). d One drop of water was added. S4

A 10 ml round-bottom flask was charged with tosylhydrazone (1 mmol), Cu(OAc) 2 H 2 O (0.15 mmol) and xylene (3 ml). Then, the flask was degassed for 30 seconds, and then was filled with argon gas and stirred at 90 to 140 o C for 2-3 h under 1 atm argon. When the reaction was completed (detected by TLC), the mixture was cooled to room temperature and the resulting mixture was filtered through a small pad of aluminum oxide (neutrality) and concentrated in vacuo. The products were separated by aluminum oxide column chromatography (neutrality) (hexanes/ CH 2 Cl 2 = 20: 1 to 4: 1). 4. General procedure B (Synthesis of alkynes from N-tosylhydrazones) (3a-3f): A 10 ml round-bottom flask was charged with tosylhydrazone (1 mmol), Cu(OAc) 2 H 2 O (0.15 mmol) and xylene (3 ml). Then, the flask was degassed for 30 seconds, and then was filled with argon gas and stirred at 90 to 140 o C for 2-3 h under 1 atm argon. When the reaction was completed (detected by TLC), the solution was evaporated to dryness under reduced pressure. Subsequently, t-buok (3 mmol) and dry THF (5 ml) were added the reaction at 70 C for 1 h. The reaction mixture was cooled to room temperature, concentrated, and extracted with CH 2 Cl 2 (3 10 ml). The combined organic layers were washed with brine, dried, filtered, and evaporated to afford crude products under reduced pressure. Purification on silica gel (hexanes/ EtOAc = 100: 1 to 50: 1) afforded compounds 3. S5

5. General Procedure C (The Reaction Mechanism): A 10 ml round-bottom flask was charged with tosylhydrazone (1 mmol), Cu(OAc) 2 H 2 O (0.15 mmol), TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) (2 mmol) and xylene (5 ml). Then, the flask was degassed for 30 seconds, and filled with argon gas, then stirred at 90 o C for 3 h under 1 atm argon. Upon completion, the mixture was cooled to room temperature and filtered through a small pad of silica gel. The filtrate was concentrated in vacuo, and the crude residue was purified by chromatography on a silica gel column to afford 4a and 4b. A 10 ml round-bottom flask was charged with tosylhydrazone (1 mmol), Cu(OAc) 2 H 2 O (0.15 mmol), DPE (1,1-diphenylethylene) (2 mmol) and xylene (5 ml). Then, the flask was degassed for 30 seconds, and then was filled with argon gas and stirred at 90 o C for 2.5 h under 1 atm argon. Upon completion, the mixture was cooled to room temperature and the resulting mixture was concentrated in vacuo. The crude residue was purified by aluminum oxide column chromatography (neutrality) to afford 5a and 1a. S6

6. Compound characterization: (E)-(1-tosylethene-1,2-diyl)dibenzene (2a): 1 (procedure A) 93% yield, 311 mg; white solid; mp 173-175 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.95 (s, 1H), 7.50 (d, J = 7.8 Hz, 2H), 7.35 (d, J = 7.2 Hz, 1H), 7.31 7.25 (m, 2H), 7.23 (d, J = 7.2 Hz, 1H), 7.20 7.13 (m, 4H), 7.08 7.01 (m, 4H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.2, 141.5, 137.3, 135.7, 132.9, 131.4, 130.8, 130.6, 130.0, 129.4, 129.2, 128.9, 128.7, 128.5, 21.7; HRMS (ESI) m/z calculated for C 21 H 18 O 2 SNa [M+Na] + : 357.0920; found 357.0923. (E)-1-methyl-4-(2-phenyl-2-tosylvinyl)benzene (2b): 1 (procedure A) 87% yield, 303 mg; white solid; mp 144-145 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.92 (s, 1H), 7.50 (d, J = 7.7 Hz, 2H), 7.35 (d, J = 7.1 Hz, 1H), 7.28 (t, J = 8.0 Hz, 2H), 7.17 (d, J = 7.7 Hz, 2H), 7.03 (d, J = 7.2 Hz, 2H), 6.96 (s, 4H), 2.37 (s, 3H), 2.25 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.0, 140.5, 140.3, 137.4, 135.9, 131.6, 130.8, 130.5, 130.0, 129.4, 129.3, 129.1, 128.8, 128.6, 21.7, 21.4; HRMS (ESI) m/z calculated for C 22 H 20 O 2 SNa [M+Na] + : 371.1076; found 371.1086. S7

(E)-1-fluoro-4-(2-phenyl-2-tosylvinyl)benzene (2c): (procedure A) 93% yield, 327 mg; white solid; mp 182-183 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.91 (s, 1H), 7.49 (d, J = 7.3 Hz, 2H), 7.37 (d, J = 6.7 Hz, 1H), 7.33 7.25 (m, 2H), 7.19 (d, J = 7.2 Hz, 2H), 7.10 6.95 (m, 4H), 6.85 (t, J = 8.0 Hz, 2H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 163.5 (d, J F-C = 251 Hz), 144.2, 141.2, 137.8, 136.0, 135.6, 132.5 (d, J F-C = 9 Hz), 131.2, 130.7, 129.4, 129.3, 129.0, 128.7, 115.7 (d, J F-C = 18 Hz), 21.7; HRMS (ESI) m/z calculated for C 21 H 17 FO 2 SNa [M+Na] + : 375.0825; found 375.0842; IR (KBr): 3050, 2919, 1635, 1596, 1502, 1444, 1375, 1305, 1228, 1144, 1087, 955, 915, 840, 807, 754, 689, 667, 600, 564 cm -1. (E)-1-chloro-4-(2-phenyl-2-tosylvinyl)benzene (2d): (procedure A) 87% yield, 320 mg; white solid; mp 179-180 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.89 (s, 1H), 7.49 (d, J = 7.6 Hz, 2H), 7.36 (d, J = 7.0 Hz, 1H), 7.29 (t, J = 8.0 Hz, 2H), 7.18 (d, J = 7.7 Hz, 2H), 7.13 (d, J = 8.1 Hz, 2H), 7.00 (dd, J = 12.5 Hz, 8.2 Hz, 4H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.3, 142.2, 136.0, 135.8, 135.5, 131.7, 131.4, 131.1, 130.6, 129.5, 129.4, 129.0, 128.8, 128.7, 21.9; HRMS (ESI) m/z calculated for C 21 H 17 ClO 2 SNa [M+Na] + : 391.0530; found 391.0535; IR (KBr): 3063, 2921, 1670, 1634, 1592, 1487, 1444, 1307, 1142, 1086, 1017, 957, 917, 837, 812, 746, 674, 600, 555 cm -1. S8

(E)-1-bromo-4-(2-phenyl-2-tosylvinyl)benzene (2e): (procedure A) 80% yield, 330 mg; white solid; mp 161-162 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.87 (s, 1H), 7.49 (d, J = 6.8 Hz, 2H), 7.36 (d, J = 6.4 Hz, 1H), 7.29 (s, 4H), 7.19 (d, J = 6.7 Hz, 2H), 7.01 (d, J = 6.2 Hz, 2H), 6.91 (d, J = 7.1 Hz, 2H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.3, 142.3, 135.9, 135.4, 131.9, 131.80, 131.78, 131.0, 130.6, 129.5, 129.4, 129.0, 128.7, 124.4, 21.7; HRMS (ESI) m/z calculated for C 21 H 17 BrO 2 SNa [M+Na] + : 435.0025; found 435.0026; IR (KBr): 3051, 2920, 1628, 1590, 1486, 1445, 1309, 1142, 1080, 1010, 953, 920, 813, 672, 599, 550 cm -1. (E)-1-methyl-4-(2-phenyl-1-tosylvinyl)benzene (2f): 2 (procedure A) 84% yield, 292 mg; white solid; mp 142-143 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.93 (s, 1H), 7.51 (d, J = 7.7 Hz, 2H), 7.27 7.13 (m, 6H), 7.09 (s, 3H), 6.91 (m, 2H), 2.37 (s, 3H), 2.35 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.0, 141.5, 139.1, 137.2, 135.8, 133.0, 130.51, 130.48, 129.9, 129.6, 129.4, 128.6, 128.5, 128.2, 21.7, 21.5; HRMS (ESI) m/z calculated for C 22 H 20 O 2 SNa [M+Na] + : 371.1076; found 371.1093. S9

(E)-1-(1-(4-methoxyphenyl)-2-phenylvinylsulfonyl)-4-methylbenzene (2g): 3 (procedure A) 82% yield, 298 mg; white solid; mp 170-171 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.92 (s, 1H), 7.51 (d, J = 7.0 Hz, 2H), 7.27 7.15 (m, 5H), 7.11 (s, 2H), 6.96 (d, J = 7.3 Hz, 2H), 6.82 (d, J = 7.3 Hz, 2H), 3.82 (s, 3H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 160.2, 144.1, 141.3, 137.3, 135.9, 133.1, 132.1, 130.6, 129.9, 129.4, 128.7, 128.5, 123.2, 114.4, 55.3, 21.7; HRMS (ESI) m/z calculated for C 22 H 20 O 3 SNa [M+Na] + : 387.1025; found 387.1039; IR (KBr): 3060, 2921, 1600, 1508, 1448, 1444, 1308, 1249, 1142, 1084, 1027, 957, 920, 832, 757, 693, 665, 568, 537 cm -1. (E)-1-fluoro-4-(2-phenyl-1-tosylvinyl)benzene (2h): (procedure A) 86% yield, 303 mg; white solid; mp 215-216 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.96 (s, 1H), 7.50 (d, J = 7.7 Hz, 2H), 7.25 (d, J = 7.4 Hz, 1H), 7.20 (d, J = 7.6 Hz, 4H), 7.07 (d, J = 7.8 Hz, 2H), 7.04 6.93 (m, 4H), 2.38 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 163.1 (d, J F-C = 210 Hz), 144.3, 140.4, 137.8, 135.5, 132.7 (d, J F-C = 8 Hz), 132.6, 130.5, 130.2, 129.5, 128.6, 128.6, 127.3 (d, J F-C = 3 Hz), 116.2 (d, J F-C = 22 Hz), 21.6; HRMS (ESI) m/z calculated for C 21 H 17 FO 2 SNa [M+Na] + : 375.0825; found 375.0827; IR (KBr): 3051, 2922, 1635, 1596, 1502, 1445, 1409, 1300, 1221, 1144, 1087, 1020, 948, 911, 827, 809, 777, 699, 667, 595, 563, 504 cm -1. S10

(E)-1-chloro-4-(2-phenyl-1-tosylvinyl)benzene (2i): 3 (procedure A) 88% yield, 324 mg; white solid; mp 234-235 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.96 (s, 1H), 7.50 (d, J = 6.8 Hz, 2H), 7.35 7.15 (m, 7H), 7.07 (d, J = 6.3 Hz, 2H), 6.99 (d, J = 7.3 Hz, 2H), 2.40 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 140.3, 137.9, 135.5, 132.6, 132.2, 131.7, 130.6, 130.3, 129.9, 129.6, 129.3, 128.7, 128.6, 21.7; HRMS (ESI) m/z calculated for C 21 H 17 ClO 2 SNa [M+Na] + : 391.0530; found 391.0540; IR (KBr): 3050, 2921, 1631, 1592, 1487, 1441, 1401, 1306, 1221, 1142, 1083, 1014, 950, 906, 817, 702, 591, 553, 498 cm -1. (E)-1-bromo-4-(2-phenyl-1-tosylvinyl)benzene (2j): (procedure A) 86% yield, 354 mg; white solid; mp 234-235 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.95 (s, 1H), 7.50 (d, J = 7.0 Hz, 2H), 7.43 (d, J = 7.3 Hz, 2H), 7.32 7.15 (m, 5H), 7.07 (d, J = 6.6 Hz, 2H), 6.92 (d, J = 6.8 Hz, 2H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 140.4, 137.9, 132.6, 135.5, 132.4, 132.2, 131.8, 130.5, 130.3, 129.6, 128.7, 128.6, 123.8, 21.7; HRMS (ESI) m/z calculated for C 21 H 17 BrO 2 SNa [M+Na] + : 435.0025; found 435.0038; IR (KBr): 3048, 2917, 1630, 1591, 1484, 1441, 1399, 1306, 1141, 1081, 1010, 950, 906, 815, 701, 672, 589, 550, 493 cm -1. S11

(E)-1-bromo-3-(2-phenyl-1-tosylvinyl)benzene (2k): (procedure A) 85% yield, 350 mg; white solid; mp 135-136 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.95 (s, 1H), 7.51 (d, J = 7.3 Hz, 3H), 7.30 7.13 (m, 7H), 7.07 (d, J = 7.4 Hz, 2H), 6.96 (d, J = 7.3 Hz, 1H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.5, 140.1, 137.8, 135.3, 133.5, 133.4, 132.4, 132.3, 130.5, 130.3, 130.3, 129.5, 129.5, 128.6, 128.6, 122.6, 21.7; HRMS (ESI) m/z calculated for C 21 H 17 BrO 2 SNa [M+Na] + : 435.0025; found 435.0025; IR (KBr): 3050, 2919, 1675, 1627, 1592, 1559, 1490, 1444, 1405, 1306, 1207, 1141, 1082, 950, 818, 743, 684, 609, 544, 467 cm -1. (E)-1-bromo-2-(2-phenyl-1-tosylvinyl)benzene (2l): (procedure A) 56% yield, 231 mg; white solid; mp 99-100 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 8.01 (s, 1H), 7.48 (t, J = 8.1 Hz, 3H), 7.38 (d, J = 5.1 Hz, 2H), 7.27 (d, J = 7.8 Hz, 2H), 7.19 (d, J = 6.3 Hz, 4H), 7.07 (d, J = 7.3 Hz, 2H), 2.39 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 139.2, 139.0, 135.5, 133.19, 133.16, 132.9, 132.0, 130.8, 130.4, 130.1, 129.4, 129.1, 128.7, 127.7, 125.3, 21.7; HRMS (ESI) m/z calculated for C 21 H 17 BrO 2 SNa [M+Na] + : 435.0025; found 435.0041; IR (KBr): 3053, 2921, 1677, 1619, 1577, 1494, 1439, 1318, 1148, 1094, 1018, 906, 800, 745, 696, 545 cm -1. S12

(E)-1-nitro-4-(2-phenyl-1-tosylvinyl)benzene (2m): (procedure A) 93% yield, 352 mg; yellow solid; mp 99-100 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 8.15 (d, J = 8.5 Hz, 2H), 8.03 (s, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.32 7.18 (m, 7H), 7.03 (d, J = 7.6 Hz, 2H), 2.41 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 148.1, 144.8, 139.6, 138.8, 138.6, 135.2, 132.0, 130.6, 130.5, 129.7, 128.8, 128.5, 123.9, 77.4, 21.65; HRMS (ESI) m/z calculated for C 21 H 17 NO 4 SNa [M+Na] + : 402.0770; found 402.0760; IR (KBr): 3052, 2922, 1629, 1595, 1516, 1348, 1306, 1142, 1085, 934, 855, 814, 677, 556 cm -1. (E)-2-methyl-5-(2-phenyl-2-tosylvinyl)thiophene (2n): (procedure A) 81% yield, 287 mg; yellow solid; mp 108-109 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 8.02 (s, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.45 7.39 (m, 1H), 7.34 (d, J = 7.5 Hz, 2H), 7.27 7.22 (m, 1H), 7.19 (d, J = 7.9 Hz, 2H), 7.05 (d, J = 3.3 Hz, 1H), 7.00 (d, J = 7.3 Hz, 1H), 6.62 (d, J = 2.8 Hz, 1H), 2.39 (s, 3H), 2.29 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 146.7, 144.0, 136.6, 136.2, 134.9, 134.6, 131.7, 131.5, 130.8, 129.6, 129.4, 129.1, 128.6, 125.6, 21.7, 15.7; HRMS (ESI) m/z calculated for C 20 H 18 O 2 S 2 Na [M+Na] + : 377.0640; found 377.0645; IR (KBr): 3052, 2919, 1675, 1617, 1529, 1490, 1447, 1292, 1220, 1141, 1082, 938, 899, 804, 700, 663, 595 cm -1. S13

(E)-1-methyl-4-(1-phenylprop-1-en-2-ylsulfonyl)benzene (2o): 1 (procedure A) 81% yield, 220 mg; yellow solid; mp 103-104 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.81 (d, J = 7.3 Hz, 3H), 7.39 (s, 4H), 7.34 (d, J = 8.0 Hz, 3H), 2.43 (s, 3H), 2.11 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.3, 137.5, 137.0, 136.0, 133.8, 129.9, 129.6, 129.3, 128.7, 128.2, 21.6, 13.2; HRMS (ESI) m/z calculated for C 16 H 16 O 2 SNa [M+Na] + : 295.0763; found 295.0770. (E)-1-bromo-4-(2-tosylprop-1-enyl)benzene (2p): (procedure A) 72% yield, 252 mg; yellow solid; mp 69-70 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.80 (d, J = 7.9 Hz, 2H), 7.72 (s, 1H), 7.53 (d, J = 8.2 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.25 (d, J = 8.2 Hz, 2H), 2.44 (s, 3H), 2.08 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.5, 138.4, 135.8, 135.7, 132.7, 131.9, 131.1, 129.9, 128.3, 123.6, 21.7, 13.2; HRMS (ESI) m/z calculated for C 16 H 15 BrO 2 SNa [M+Na] + : 372.9868; found 372.9874. IR (KBr): 3052, 2920, 1645, 1590, 1488, 1404, 1292, 1148, 1074, 1009, 815, 750, 671, 569 cm -1. (E)-1,2-diphenyl-1-(phenylsulfonyl)ethene (2q): 4 (procedure A) 94% yield, 301 mg; white solid; mp 176-178 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.97 (s, 1H), 7.63 (d, J = 7.4 Hz, 2H), 7.55 7.49 (m, 1H), 7.44 7.34 (m, 3H), 7.31 7.21 (m, 3H), 7.19 7.13 (t, J = 8.0 Hz, 2H), 7.07 (d, J = 7.3 Hz, 2H), 7.02 (d, J = 7.2 Hz, 2H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 141.2, 138.6, S14

137.6, 133.2, 132.7, 131.2, 130.7, 130.6, 130.1, 129.2, 128.9, 128.7, 128.6, 128.5; HRMS (ESI) m/z calculated for C 20 H 16 O 2 SNa [M+Na] + : 343.0763; found 343.0767. (E)-(1-(4-fluorophenylsulfonyl)ethene-1,2-diyl)dibenzene (2r): 4 (procedure A) 95% yield, 321 mg; white solid; mp 162-164 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.97 (s, 1H), 7.66 7.56 (m, 2H), 7.42 7.35 (m, 1H), 7.30 (t, J = 6.0 Hz, 2H), 7.24 (d, J = 7.1 Hz, 2H), 7.16 (t, J = 6.0 Hz, 2H), 7.10 7.01 (m, 6H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 166.7 (d, J F-C = 255 Hz ), 141.1, 137.7, 134.7 (d, J F-C = 3 Hz ), 132.6, 131.4 (d, J F-C = 9 Hz ), 131.1, 130.7, 130.6, 130.2, 129.3, 129.0, 128.5, 116.1 (d, J F-C = 22 Hz ); HRMS (ESI) m/z calculated for C 20 H 15 FO 2 SNa [M+Na] + : 361.0669; found 361.0671. (E)-1-methyl-4-(styrylsulfonyl)benzene (2s): 5 (procedure A) 85% yield, 219 mg (E/Z = 38:1); white solid; mp 102-103 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.83 (d, J = 7.7 Hz, 2H), 7.66 (d, J = 15.4 Hz, 1H), 7.48 (d, J = 5.6 Hz, 2H), 7.42 7.32 (m, 5H), 6.85 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 142.0, 137.8, 132.5, 131.2, 130.0, 129.1, 128.6, 127.8, 127.6, 21.7; HRMS (ESI) m/z calculated for C 15 H 14 O 2 SNa [M+Na] + : 281.0607; found 281.0609. S15

(E)-1-methyl-2-(2-tosylvinyl)benzene (2t): 6 (procedure A) 71% yield, 193 mg (E/Z = 36:1); white solid; mp 70-71 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.86 (d, J = 15.3 Hz, 1H), 7.75 (d, J = 7.9 Hz, 2H), 7.35 (d, J = 7.5 Hz, 1H), 7.27 (d, J = 7.8 Hz, 2H), 7.23 7.18 (m, 1H), 7.14 7.08 (m, 2H), 6.70 (d, J = 15.3 Hz, 1H), 2.37 (s, 3H), 2.36 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 139.6, 138.2, 137.7, 131.4, 131.1, 130.9, 130.0, 128.5, 127.8, 126.9, 126.5, 21.7, 19.9; HRMS (ESI) m/z calculated for C 16 H 16 O 2 SNa [M+Na] + : 295.0763; found 295.0767. (E)-1-methoxy-3-(2-tosylvinyl)benzene (2u): 7 (procedure A) 74% yield, 213 mg (E/Z = 10:1); colorless gum. 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.83 (d, J = 8.0 Hz, 2H), 7.62 (d, J = 15.3 Hz, 1H), 7.34 (d, J = 7.9 Hz, 2H), 7.28 (d, J = 8.0 Hz, 1H), 7.06 (d, J = 7.5 Hz, 1H), 6.99 6.93 (m, 2H), 6.84 (d, J = 15.3 Hz, 1H), 3.81 (s, 3H), 2.43 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 160.0, 144.5, 141.9, 137.7, 133.8, 130.1, 130.0, 127.9, 127.8, 121.2, 117.1, 113.3, 55.4, 21.7; HRMS (ESI) m/z calculated for C 16 H 16 O 3 SNa [M+Na] + : 311.0712; found 311.0716. (E)-1-(4-chlorostyrylsulfonyl)-4-methylbenzene (2v): 7 (procedure A) 83% yield, 242 mg (E/Z = 17:1); white solid; mp 135-136 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.82 (d, J = 8.0 Hz, 2H), 7.60 (d, J = 15.4 Hz, 1H), 7.45 7.39 (m, 2H), 7.38 7.29 (m, 4H), 6.83 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.7, 140.5, 137.5, 137.2, 131.0, 130.1, 129.8, 129.4, 128.2, 127.8, 21.7; HRMS (ESI) m/z calculated for C 15 H 13 ClO 2 SNa [M+Na] + : 315.0217; found 315.0226. S16

(E)-1-methyl-4-(4-methylstyrylsulfonyl) benzene (2w): 7 (procedure A) 79% yield, 215 mg (E/Z > 95:1); white solid; mp 91-92 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.82 (d, J = 7.8 Hz, 2H), 7.63 (d, J = 15.4 Hz, 1H), 7.36 (dd, J = 11.3 Hz, 8.3 Hz, 4H), 7.19 (d, J = 7.5 Hz, 2H), 6.79 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H), 2.37 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 142.1, 141.8, 137.9, 130.0, 129.9, 129.7, 128.6, 127.7, 126.3, 21.7, 21.6; HRMS (ESI) m/z calculated for C 16 H 16 O 2 SNa [M+Na] + : 295.0763; found 295.0762. (E)-1-(3-bromostyrylsulfonyl)-4-methylbenzene (2x): 6 (procedure A) 86% yield, 289 mg (E/Z = 15:1); yellow solid; mp 62-63 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.82 (d, J = 7.8 Hz, 2H), 7.59 (d, J = 5.7 Hz, 1H), 7.56 (d, J = 5.2 Hz, 1H), 7.51 (d, J = 7.5 Hz, 1H), 7.44 (s, 1H), 7.39 7.30 (m, 2H), 7.29 7.20 (m, 1H), 6.86 (d, J = 15.4 Hz, 1H), 2.43 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.7, 140.1, 137.3, 134.5, 133.9, 131.1, 130.6, 130.1, 129.2, 127.8, 127.2, 123.1, 21.7; HRMS (ESI) m/z calculated for C 15 H 13 BrO 2 SNa [M+Na] + : 358.9712; found 358.9727. S17

(E)-1-(4-fluorostyrylsulfonyl)-4-methylbenzene (2y): 7 (procedure A) 89% yield, 246 mg (E/Z = 10:1); white solid; mp 84-85 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.83 (d, J = 7.5 Hz, 2H), 7.62 (d, J = 15.4 Hz, 1H), 7.50 7.45 (m, 2H), 7.35 (d, J = 7.5 Hz, 2H), 7.08 (t, J = 7.9 Hz, 2H), 6.79 (d, J = 15.4 Hz, 1H), 2.44 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 164.3 (d, J F-C = 252 Hz), 144.5, 140.7, 137.7, 130.6 (d, J F-C = 8 Hz), 130.1, 128.8 (d, J F-C = 3 Hz), 127.8, 127.4 (d, J F-C = 3 Hz), 116.3 (d, J F-C = 22 Hz), 21.7; HRMS (ESI) m/z calculated for C 15 H 13 FO 2 SNa [M+Na] + : 299.0512; found 299.0517. (E)-2-(2-tosylvinyl)naphthalene (2z): 8 (procedure A) 76% yield, 219 mg (E/Z = 60:1); yellow solid; mp 99-100 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.89 7.77 (m, 7H), 7.52 7.49 (m, 3H), 7.33 (d, J = 7.9 Hz, 2H), 6.95 (d, J = 15.4 Hz, 1H), 2.41 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.4, 142.0, 137.8, 134.5, 133.1, 130.9, 130.0, 129.9, 128.9, 128.7, 127.8, 127.75, 127.74, 127.67, 127.0, 123.4, 21.6; HRMS (ESI) m/z calculated for C 19 H 15 O 2 SNa [M+Na] + : 331.0763; found 331.0768. (E)-1-(2-tosylvinyl)naphthalene (2z ): 9 (procedure A) 81% yield, 249 mg (E/Z > 95:1); colorless gum. 1 H NMR (400 MHz, CDCl 3, ppm) δ: 8.49 (d, J = 15.2 Hz, 1H), 8.14 (d, J = 8.3 Hz, 1H), 7.88 (d, J = 8.0 Hz, 4H), 7.65 7.59 (m, 1H), 7.57 (d, J = 7.7 Hz, 1H), 7.53 (d, J = 7.5 Hz, 1H), 7.42 (t, J = 7.8 Hz, 1H), 7.34 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 15.2 Hz, 2H), 2.41 (s, 3H); 13 C NMR (100 MHz, CDCl 3, ppm) δ: 144.5, 138.9, 137.6, 133.6, 131.4, 131.2, 130.0, 129.9, 129.5, 128.8, 127.8, 127.3, 126.5, 125.6, 125.3, 123.0, 21.6; HRMS (ESI) m/z calculated for S18

C 19 H 16 O 2 SNa [M+Na] + : 331.0763; found 331.0778. (E)-4-methyl-N'-(1-o-tolylethylidene)benzenesulfonohydrazide (E-1t): 10 40% yield, 121 mg; yellow solid; mp 131-132 o C; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 8.33 (d, J = 7.8 Hz, 2H), 7.91 7.83 (m, 3H), 7.79 (d, J = 7.3 Hz, 2H), 7.72 (s, 1H), 7.37 (d, J = 7.1 Hz, 1H), 3.00 (s, 3H), 2.70 (s, 3H), 2.56 (s, 3H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 156.0, 144.0, 135.4, 134.3, 133.3, 131.1, 129.7, 129.6, 127.7, 127.0, 126.0, 24.6, 21.6, 18.5. (Z)-4-methyl-N'-(1-o-tolylethylidene)benzenesulfonohydrazide (Z-1t): 10 60% yield, 181 mg; white solid; mp 139-140 o C; 1 H NMR (400 MHz, DMSO-d 6, ppm) δ: 10.54 (s, 1H), 7.79 (d, J = 6.6 Hz, 2H), 7.37 (d, J = 6.6 Hz, 2H), 7.17 (d, J = 10.8 Hz, 4H), 2.34 (s, 3H), 2.16 (s, 3H), 2.02 (s, 3H). 13 C NMR (100 MHz, DMSO-d 6, ppm) δ: 155.9, 143.3, 138.8, 136.5, 135.2, 130.7, 129.5, 128.3, 127.8, 127.6, 125.7, 21.0, 19.9, 18.2. 1,2-diphenylethyne (3a): 1 (procedure B) 81% yield, 144 mg; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.64 7.53 (m, 4H), 7.43 7.32 (m, 6H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 131. 7, 128.4, 128.3, 123.3, 89.5. S19

1-methoxy-4-(phenylethynyl)benzene (3b): 1 (procedure B) 72% yield, 150 mg; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.53 (dd, J = 7.3 Hz, 1.7 Hz, 2H), 7.49 (d, J = 8.5 Hz, 2H), 7.35 (dd, J = 8.2 Hz, 4.8 Hz, 3H), 6.89 (d, J = 8.5 Hz, 2H), 3.83 (s, 3H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 159.7, 133.1, 131.5, 128.4, 128.0, 123.7, 115.4, 114.1, 89.4, 88.1, 55.4. ethynylbenzene (3c): 1 (procedure B) 77% yield, 79 mg; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.55 7.43 (m, 2H), 7.35 7.25 (m, 3H), 3.07 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 132.2, 128.8, 128.4, 122.2, 83.7, 77.3. 1-ethynyl-4-methoxybenzene (3d): (procedure B) 70% yield, 92 mg; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.42 (d, J = 8.9, 2H), 6.82 (d, J = 8.9, 2H), 3.78 (s, 3H), 3.00 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 160.0, 133.6, 114.2, 114.0, 83.7, 75.9, 55.3. 1-chloro-4-ethynylbenzene (3e): 11 (procedure B) 75% yield, 102 mg; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.47 7.36 (m, 2H), 7.35 7.26 (m, 2H), 3.10 (s, 1H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 135.0, 133.4, 128.7, 120.6, 82.6, 78.3. prop-1-ynylbenzene (3f): 1 (procedure B) 77% yield, 89 mg; 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.41 7.38 (m, 1H), 7.37 (d, J = 1.9 Hz, 1H), 7.26 (d, J = 2.2 Hz, 1H), 7.25 (d, J = 2.0 Hz, 2H), 2.03 (s, 3H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 131.5, 128.3, 127.6, 124.1, 85.9, 79.8, 4.3. S20

benzil (4a): 12 (procedure C) 54% yield, 113 mg; yellow solid. mp 148 149 o C. 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.97 (d, J = 7.7 Hz, 4H), 7.65 (t, J = 7.3 Hz, 2H), 7.51 (t, J = 7.5 Hz, 4H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 194.7, 135.0, 133.0, 130.0, 129.1. 1,2-diphenylethanone (4b): (procedure C) 23% yield, 45 mg; white solid. mp 54 55 o C. 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.92 (d, J = 7.7 Hz, 2H), 7.37 (t, J = 6.9 Hz, 1H), 7.28 (t, J = 7.1 Hz, 2H), 7.23 7.14 (m, 5H), 4.12 (s, 2H) ppm. 13 C NMR (100 MHz, CDCl 3, ppm) δ: 197.0, 136.1, 134.3, 132.7, 129.2, 128.2, 128.2, 128.1, 126.4, 44.9 ppm. (2-tosylethene-1,1-diyl)dibenzene (5a): 13 (procedure C) 72% yield, 240 mg; white solid. mp 94 95 o C. 1 H NMR (400 MHz, CDCl 3, ppm) δ: 7.47 (d, J = 8.0 Hz, 2H), 7.41 7.34 (m, 2H), 7.30 (t, J = 7.4 Hz, 4H), 7.20 (d, J = 7.5 Hz, 2H), 7.15 (d, J = 7.9 Hz, 2H), 7.10 (d, J = 7.3 Hz, 2H), 6.99 (s, 1H), 2.38 (s, 3H). 13 C NMR (100 MHz, CDCl 3, ppm) δ: 154.8, 143.8, 139.3, 138.6, 135.6, 130.3, 129.8, 129.4, 129.0, 128.9, 128.6, 128.3, 127.9, 127.8, 21.6. S21

7. References (1) Ojha, D. P.; Prabhu, K. R. Org. Lett. 2015, 17, 18. (2) Naik, P. J.; Kumar, L. V.; Naveen, M.; Reddy, A. B.; Sree, M. K.; Penchalaiah, N.; Swamy, G. N. Indian J. Chem., Sect B 2012, 51, 765. (3) Reddy, A. B.; Hymavathi, A.; Kumar, L. V.; Penchalaiah, N.; Naik, P. J.; Karunasree, M.; Swamy, G. N. Pharma Chemica 2010, 2, 438. (4) Chang, M.-Y.; Chen, Y.-C.; Lin, S.-Y.; Chan, C.-K. Tetrahedron 2014, 70, 1740. (5) Jiang, Q.; Xu, B.; Jia, J.; Zhao, A.; Zhao, Y.-R.; Li, Y.-Y.; He, N.-N.; Guo, C.-C. J. Org. Chem. 2014, 79, 7372. (6) Tang, S.; Wu, Y.; Liao, W.; Bai, R.; Liu, C.; Lei. A. Chem. Commun. 2014, 50, 4496. (7) Guo, R.; Gui, Q.; Wang, D.; Tan, Z. Catal. Lett. 2014, 144, 1377. (8) Li, X.; Xu, Y.; Wu, W.; Jiang, C.; Qi, C.; Jiang, H. Chem. Eur. J. 2014, 20, 7014 (9) Nair, V.; Augustine, A.; Panicker, S. B.; Suja, T. D.; Mathai, S. Res. Chem. Intermed. 2003, 29, 213. (10) Cai, Z.-J.; Lu, X.-M.; Zi, Y.; Yang, C.; Shen, L.-J.; Li, J.; Wang, S.-Y.; Ji, S.-J. Org. Lett. 2014, 16, 5108. (11) Jepsen, T. H.; Kristensen, J. L. J. Org. Chem. 2014, 79, 9423. (12) Daw, P.; Petakamsetty, R.; Sarbajna, A.; Laha, S.; Ramapanicker, R.; Bera, J. K. J. Am. Chem. Soc. 2014, 136, 13987. (13) Reeves, D. C.; Rodriguez, S.; Lee, H.; Haddad, N.; Krishnamurthy, D.; Senanayake, C. H. Tetrahedron Lett. 2009, 50, 2870. S22

8. Spectral data S23