Supporting Information

Supporting Information Wiley-VCH 2014 69451 Weinheim, Germany Copper-Catalyzed Coupling of Oxime Acetates with Sodium Sulfinates: An Efficient Synthesis of Sulfone Derivatives** Xiaodong Tang, Liangbin Huang, Yanli Xu, Jidan Yang, Wanqing Wu, and Huanfeng Jiang* ange_201311217_sm_miscellaneous_information.pdf

Supporting Information Table of Contents General Information...[1] Typical Procedure for the Preparation of Oxime Acetates.....[1] Experimental Section for products 3 and 4 [1] Characterization Data for All Products...[1] A single crystal of product 3ta....[7] References..........[7] NMR Spectra for All Compounds.................. [8]

General Information 1 H and 13 C NMR spectra were recorded on BRUKER DRX-400 spectrometer using CDCl 3 as solvent and TMS as an internal standard. Gas chromatograph mass spectra were obtained with a SHIMADZU model GCMS-QP5000 spectrometer. High-resolution mass spectra (ESI) were obtained with a LCMS-IT-TOF mass spectrometer. Unless otherwise stated, all reagents and solvents were purchased from commercial suppliers and used without further purification. Oxime acetates were synthesized according to the literature procedure. Typical Procedure for the Preparation of Oxime Acetates The mixture of ketoxime (3.0 mmol) and acetic anhydride (6.0 mmol) was stirred at 105 o C for 3 h. The reaction mixture was cooled to room temperature, diluted with EtOAc (25 ml) and washed with H 2 O (20 ml) and brine (10 ml). The organic layers were dried over anhydrous Na 2 SO 4 and evaporated in vacuum. The residue was purified by column chromatography on silica gel to afford the oxime acetates 1 with hexanes/ethyl acetate as the eluent. Experimental Section for products 3 and 4 General procedure for products 3: oxime acetates (0.5 mmol), sodium sulfinates (0.5 mmol), Cu(OAc) 2 (10 mol %), in DMSO (2 ml) were added to a 25 ml Schlenk tube with magnetic stirrer bar. The mixture was stirred at 100 C (oil bath temperature) for 6 h under N 2. After the reaction was finished (monitored by TLC), the mixture was cooled to room temperature and quenched with aqueous MgSO 4 and the solvent was removed under vacuum. The crude product was purified by flash column chromatography (EtOAc/hexanes) on silica gel. General procedure for products 4: oxime acetates (0.5 mmol), sodium sulfinates (0.5 mmol), Cu(OAc) 2 (10 mol %), in DMSO (2 ml) were added to a 25 ml Schlenk tube with magnetic stirrer bar. The mixture was stirred at 100 C (oil bath temperature) for 6 h under N 2. After the reaction was finished (monitored by TLC), the mixture was cooled to room temperature and quenched with aqueous MgSO 4 and the solvent was removed under vacuum. Then, the residue was stirred with silica gel in methylene dichloride at room temperature overnight. The resulting mixture was filtered and concentrated, and then the crude product was purified by column chromatography on silica gel using petroleum ether/etoac as eluent to provide the pure target product. Characterization data for all products NH 2 Ts (Z)-1-phenyl-2-tosylethenamine (3aa) 1 H NMR (400 MHz, DMSO) δ 7.84 (d, J = 8.2 Hz, 2H), 7.55 (d, J = 5.7 Hz, 2H), 7.49 7.41 (m, 3H), 7.37 (d, J = 8.1 Hz, 2H), 7.11 (s, 2H), 5.15 (s, 1H), 2.36 (s,3h). 13 C NMR (100 MHz, DMSO) δ 156.2, 142.5, 142.2, 136.0, 130.6, 129. 5, 128.6, 126.7, 125.5, 89.7, 20.9. IR (KBr) ν (cm -1 ) 3459, 3360, 2925, 1622, 1286, 1134, 697. MS (EI, 70 ev) m/z (%): 273 (M+), 209, 193, 104, 91, 65. HRMS-ESI (m/z): calcd for C 15 H 15 NSO 2, [M+H]+ : 274.0896; found, 274.0908. (Z)-1-(o-tolyl)-2-tosylethenamine (3ja) 1 H NMR (400 MHz, CDCl 3 ) δ 7.84 (d, J = 8.2 Hz, 2H), 7.30 (d, J = 8.1 Hz, 2H), 7.27 7.24 (m, 1H), 7.22 7.12 (m, 3H), 4.78 (s, 1H), 2.43 (s, 3H), 2.29 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 156.4, 143.0, 141.7, 137.2, 135.1, 130.7, 129. 6, 129.5, 127.8, 126.0, 93.5, 21.5, 19.2. IR (KBr) ν (cm -1 ) 3449, 3346, 1615, 1386, 1289,1131, 864. MS (EI, 70 ev) m/z (%): 387 (M+), 148, 132, 115, 91, 77. HRMS-ESI (m/z): calcd for C 16 H 17 NSO 2, [M+Na]+ : 310.0872; found, 310.0884. 1

(Z)-1-(2-chlorophenyl)-2-tosylethenamine (3ka) 1 H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 7.8 Hz, 2H), 7.41 7.28 (m, 6H), 4.85 (s, 1H), 2.42 (s, 3H). 13C NMR (101 MHz, CDCl3) δ 153.9, 143.2, 141.3, 136.1, 131.6, 130.8, 130.2, 129.8, 129.5, 127.1, 126.1, 94.6, 21.5. IR (KBr) ν (cm-1) 3449, 3347, 1617, 1133, 862. MS (EI, 70 ev) m/z (%): 307 (M+), 272, 207, 133, 89, 77. HRMS-ESI (m/z): calcd for C15H14ClNSO2, [M+Na]+ : 330.0326; found, 330.0327. (Z)-1-(2-bromophenyl)-2-tosylethenamine (3la) 1 H NMR (400 MHz, CDCl3) δ 7.74 (d, J = 8.2 Hz, 2H), 7.42 (t, J = 7.7 Hz, 1H), 7.26 7.11 (m, 5H), 4.66 (s, 1H), 2.32 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.3, 143.2, 141.2, 138.1, 133.3, 131.0, 129.8, 129.6, 127.6, 126.1, 120.8, 94.1, 21.6. IR (KBr) ν (cm-1) 3449, 3346, 1618, 1131, 832, 684. MS (EI, 70 ev) m/z (%): 353 (M+), 272, 193, 133, 117, 89, 65. HRMS-ESI (m/z): calcd for C15H14BrNSO2, [M+Na]+ : 373.9821; found, 373.9829. Ts H2N (Z)-1-(naphthalen-1-yl)-2-tosylethenamine (3ta) 1 H NMR (400 MHz, CDCl3) δ 8.04 8.01 (m, 1H), 7.89 7.80 (m, 4H), 7.52 7.38 (m, 4H), 7.32 (d, J = 8.1 Hz, 2H), 4.97 (s, 1H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 155.6, 143.1, 141.7, 135.0, 133.6, 130.1, 130.1, 129.7, 128. 5, 127.0, 126.4, 126.0, 125.7, 125.0, 124.8, 94. 5, 21.6. IR (KBr) ν (cm-1) 3741, 1707, 1514, 1292, 778. MS (EI, 70 ev) m/z (%): 323 (M+), 258, 207, 168, 141, 91, 65. HRMS-ESI (m/z): calcd for C19H17NSO2, [M+Na]+ : 346.0872; found, 346.0878. 1-phenyl-2-tosylethanone (4aa)1 1 H NMR (400 MHz, CDCl3) δ 7.94 (d, J = 7.7 Hz, 2H), 7.76 (d, J = 8.1 Hz, 2H), 7.61 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.7 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 4.71 (s, 2H), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 188.5, 145.4, 135.8, 135.8, 134.3, 129.8, 129.3, 128.8, 128.6, 63.3, 21.9. IR (KBr) ν (cm-1) 2926, 1679, 1319, 1150, 745. MS (EI, 70 ev) m/z (%): 274 (M+), 210, 155, 105, 91, 77. 1-(p-tolyl)-2-tosylethanone (4ba) 1 1 H NMR (400 MHz, CDCl3) δ 7.83 (d, J = 8.2 Hz, 2H), 7.75 (d, J = 8.2 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.25 (d, J = 8.0 Hz, 2H), 4.69 (s, 2H), 2.42 (s, 3H), 2.40 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.7, 145.5, 145.3, 135.9, 133.4, 129.8, 129.5, 129.5, 128.6, 63.5, 21. 8, 21.7. IR (KBr) ν (cm-1) 2925, 1678, 1322, 1154, 778. MS (EI, 70 ev) m/z (%): 288 (M+), 224, 119, 91, 65. 1-(4-methoxyphenyl)-2-tosylethanone (4ca) 1 H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.6 Hz, 2H), 7.75 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 7.9 Hz, 2H), 6.93 (d, J = 8.6 Hz, 2H), 4.66 (s, 2H), 3.87 (s, 3H), 2.42 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 186.4, 164.6, 145.2, 135.9, 131.9, 129.8, 128.9, 128. 6, 114.1, 63.5, 55.6, 21.7. IR (KBr) ν (cm-1) 3066, 2943, 1599, 1320, 1028. MS (EI, 70 ev) m/z (%): 304 (M+), 281, 240, 207, 135, 91, 77. HRMS-ESI (m/z): calcd for C16H16SO4, [M+Na]+ : 327.0662; found, 327.0668. 2

1-(4-fluorophenyl)-2-tosylethanone (4da) 1 H NMR (400 MHz, CDCl3) δ 8.03 7.95 (m, 2H), 7.74 (d, J = 8.2 Hz, 2H), 7.34 (d, J = 8.1 Hz, 2H), 7.15 (t, J = 8.5 Hz, 2H), 4.68 (s, 2H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 186.6, 166.4(d, J = 254 Hz), 145.5, 135.7, 132.3, 132.2, 129.9, 128. 6, 116.1(d, J = 22 Hz), 63.8, 21.7. IR (KBr) ν (cm-1) 2944, 1680, 1321, 1155, 1024, 811. MS (EI, 70 ev) m/z (%): 292 (M+), 228, 155, 123, 91, 65. HRMS-ESI (m/z): calcd for C15H13FSO3, [M+Na]+ : 315.0462; found, 315.0466. 1-(4-chlorophenyl)-2-tosylethanone (4ea)1 1 H NMR (400 MHz, CDCl3) δ 7.88 (d, J = 8.5 Hz, 2H), 7.73 (d, J = 8.2 Hz, 2H), 7.43 (d, J = 8.5 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 4.68 (s, 2H), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.1, 145.6, 141.0 135.7, 134.1, 130.8, 129.9, 129.2, 128.5, 63.7, 21.7. IR (KBr) ν (cm-1) 2926, 1683, 1321, 1152, 813. MS (EI, 70 ev) m/z (%): 308 (M+), 244, 155, 139, 108, 91, 65. 1-(4-bromophenyl)-2-tosylethanone(4fa) H NMR (400 MHz, CDCl3) δ 7.80 (d, J = 8.5 Hz, 2H), 7.73 (d, J = 8.2 Hz, 2H), 7.61 (d, J = 8.5 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 4.68 (s, 2H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.3, 145.6, 135.6, 134.5, 132.2, 130.8, 129.9, 128.6, 63.7, 21.7. IR (KBr) ν (cm-1) 2926, 1681, 1320, 1152, 524. MS (EI, 70 ev) m/z (%): 352 (M+), 281, 207, 193, 135, 105, 91, 73. HRMS-ESI (m/z): calcd for C15H13BrSO3, [M+Na]+ : 374.9661; found, 374.9670. 1 1-(4-iodophenyl)-2-tosylethanone (4ga) 1 H NMR (400 MHz, CDCl3) δ 7.85 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 8.1 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 4.66 (s, 2H), 2.45 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.6, 145.5, 138.2, 135.7, 135.1, 130.6, 129.9, 128.6, 102.3, 63.7, 21.7. IR (KBr) ν (cm-1) 2925, 1678, 1386, 1152, 523. MS (EI, 70 ev) m/z (%): 400 (M+), 355, 279, 176, 132, 105, 73. HRMS-ESI (m/z): calcd for C15H13ISO3, [M+Na]+ : 422.9522; found, 422.9529. 1-(4-nitrophenyl)-2-tosylethanone (4ha)4 1 H NMR (400 MHz, CDCl3) δ 8.30 (d, J = 8.7 Hz, 2H), 8.13 (d, J = 8.7 Hz, 2H), 7.74 (d, J = 8.1 Hz, 2H), 7.35 (d, J = 7.9 Hz, 2H), 4.76 (s, 2H), 2.45 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.1, 150.4, 145.9, 140.0, 135.4, 130.5, 130.1, 128.5 124.0, 64.1, 21.7. IR (KBr) ν (cm-1) 2924, 1684, 1518, 1315, 1248, 1149, 806. MS (EI, 70 ev) m/z (%): 319 (M+), 281, 224, 207, 180, 119, 91, 65. 2-tosyl-1-(4-(trifluoromethyl)phenyl)ethanone (4ia) 1 H NMR (400 MHz, CDCl3) δ 8.06 (d, J = 7.4 Hz, 2H), 7.73 (d, J = 7.4 Hz, 4H), 7.33 (d, J = 7.3 Hz, 2H), 4.74 (s, 2H), 2.44 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.5, 145.7, 138.4, 135.6, 135.2, 123.0, 129.7, 128.5, 125.9, 125.8, 63.9, 21.7. IR (KBr) ν (cm-1) 2928, 1687, 1322, 1153. MS (EI, 70 ev) m/z (%): 342 (M+), 323, 278, 173, 145, 91, 65. HRMS-ESI (m/z): calcd for C16H13F3SO4, [M+Na]+ : 365.0430; found, 365.0439. 3

1-(2-fluorophenyl)-2-tosylethanone (4ma) 1 H NMR (400 MHz, CDCl 3 ) δ 7.79 (t, J = 10.5 Hz, 3H), 7.56 (d, J = 5.5 Hz, 1H), 7.32 (d, J = 7.5 Hz, 2H), 7.28 7.20 (m, 1H), 7.15 7.06 (m, 1H), 4.78 (s, 2H), 2.43 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 185.9, 162.0(d, J = 354 Hz), 145.2, 136.3, 136.0(d, J = 9Hz), 131.2, 129.8, 128.6, 124.8(d, J = 3 Hz), 116.8(d, J = 24 Hz), 67.2, 67.1, 21.6. IR (KBr) ν (cm -1 ) 2925, 1684, 1323, 1153, 761, 512. MS (EI, 70 ev) m/z (%): 292 (M+), 228, 155, 123, 91. HRMS-ESI (m/z): calcd for C 15 H 13 FSO 3, [M+Na]+ : 315.0462; found, 315.0472. 1-(2-methoxyphenyl)-2-tosylethanone (4na) 1 H NMR (400 MHz, CDCl 3 ) δ 7.73 (d, J = 8.1 Hz, 2H), 7.64 (d, J = 7.8 Hz, 1H), 7.47 (t, J = 7.8 Hz, 1H), 7.30 7.26 (m, 2H), 6.97 (t, J = 7.5 Hz, 1H), 6.88 (d, J = 8.4 Hz, 1H), 4.91 (s, 2H), 3.85 (s, 3H), 2.40 (s, 3H). 13 C NMR (100MHz, CDCl 3 ) δ 189.2, 159.0, 144.8, 136.7, 135.2, 131.2, 129.5, 128.5, 126.3, 120.9, 111.7, 67.5, 55,7, 21.6. IR (KBr) ν (cm -1 ) 3360, 2944, 1672, 1300, 1021, 754. MS (EI, 70 ev) m/z (%): 304 (M+), 240, 207, 135, 91, 77. HRMS-ESI (m/z): calcd for C 16 H 16 SO 4, [M+Na]+ : 327.0662; found, 327.0668. 1-(m-tolyl)-2-tosylethanone (4oa) 1 H NMR (400 MHz, CDCl 3 ) δ 7.77 7.68 (m, 4H), 7.40 (d, J = 7.5 Hz, 1H), 7.33 (dd, J = 14.8, 7.7 Hz, 3H), 4.70 (s, 2H), 2.42 (s, 3H), 2.37 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 188.3, 145.3, 138.7, 135. 9, 135.8, 135.1, 129.8, 129.7, 128.7, 128.6, 126.6, 63.5, 21.7, 21.3. IR (KBr) ν (cm -1 ) 2922, 1677, 1318, 1151, 769. MS (EI, 70 ev) m/z (%): 288 (M+), 224, 155, 119, 91, 65. HRMS-ESI (m/z): calcd for C 16 H 16 SO 3, [M+Na]+ : 311.0712; found, 311.0717. 1-(3-fluorophenyl)-2-tosylethanone (4pa) 1 H NMR (400 MHz, CDCl 3 ) δ 7.75 (d, J = 8.3 Hz, 3H), 7.63 7.58 (m, 1H), 7.47 (td, J = 8.0, 5.5 Hz, 1H), 7.38 7.29 (m, 3H), 4.69 (s, 2H), 2.45 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.1, 162.8(d, J = 247 Hz), 145.6, 137.8, (d, J = 6 Hz), 135.7, 130.6(d, J = 8 Hz), 129.9, 128.6, 125.3(d, J = 3 Hz), 121.4(d, J = 21 Hz), 115.8(d, J = 23 Hz), 63.8, 21.7. IR (KBr) ν (cm -1 ) 2930, 1686, 1323, 1152, 777. MS (EI, 70 ev) m/z (%): 292 (M+), 228, 155, 123, 91, 65. HRMS-ESI (m/z): calcd for C 15 H 13 FSO 3, [M+Na]+ : 315.0462; found, 315.0472. 1-(3-chlorophenyl)-2-tosylethanone (4qa) 1 H NMR (400 MHz, CDCl 3 ) δ 7.76 (dd, J = 7.2, 1.1 Hz, 2H), 7.67 (d, J = 8.3 Hz, 2H), 7.52 7.46 (m, 1H), 7.34 (t, J = 8.2 Hz, 1H), 7.25 (d, J = 8.1 Hz, 2H), 4.61 (s, 2H), 2.36 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.1, 145.6, 137.3, 135.6, 135.2, 134.2, 130.2, 129.9, 129.1, 128.6, 127.6, 63.7, 21.7. IR (KBr) ν (cm -1 ) 2927, 1681, 1320, 1153, 772. MS (EI, 70 ev) m/z (%): 308 (M+), 244, 155, 139, 91, 65. HRMS- ESI (m/z): calcd for C 15 H 13 ClSO 3, [M+Na]+ : 331.0166; found, 331.0175. 1-(3-bromophenyl)-2-tosylethanone (4ra) 1 H NMR (400 MHz, CDCl 3 ) δ 8.00 (t, J = 1.8 Hz, 1H), 7.92 7.88 (m, 1H), 7.77 7.70 (m, 3H), 7.36 (dd, J = 15.1, 7.8 Hz, 3H), 4.67 (s, 2H), 2.45 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.0, 145.6, 137.4, 137.1, 135.6, 132.1, 130.4, 129.9, 128.6, 128.0, 123.2, 63.7, 21.7. IR 4

(KBr) ν (cm-1) 2924, 1682, 1320, 1152, 769. MS (EI, 70 ev) m/z (%): 352 (M+), 288, 207, 183, 108, 91, 65. HRMS-ESI (m/z): calcd for C15H13BrSO3, [M+Na]+ : 374.9661; found, 374.9673. 1-(3,4-dimethylphenyl)-2-tosylethanone (4sa) 1 H NMR (400 MHz, CDCl3) δ 7.75 (d, J = 7.8 Hz, 2H), 7.66 (s, 2H), 7.31 (d, J = 7.9 Hz, 2H), 7.21 (d, J = 8.4 Hz, 1H), 4.68 (s, 2H), 2.42 (s, 3H), 2.30 (s, 3H), 2.28 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 187.9, 145.2, 144.3, 137.3, 136.0, 133.8, 130.3, 130.1, 129.8, 128.6, 127.2, 63.5, 21. 7, 20.1, 19.7. IR (KBr) ν (cm-1) 2924, 1675, 1318, 1152, 863. MS (EI, 70 ev) m/z (%): 302 (M+), 238, 207, 133, 91, 77. HRMSESI (m/z): calcd for C17H18SO3, [M+Na]+ : 325.0869; found, 325.0874. 1-phenyl-2-tosylpropan-1-one (4ua) 1 H NMR (400 MHz, CDCl3) δ 7.98 (d, J = 7.9 Hz, 2H), 7.66 (d, J = 7.7 Hz, 2H), 7.61 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.4 Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 5.15 (q, J = 6.9 Hz, 1H), 2.43 (s, 3H), 1.56 (d, J = 6.9 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 192.6, 145.3, 136.3, 134.0, 133.1, 129.9, 129.5, 129.2, 128.7, 65.1, 21.7, 13.2. IR (KBr) ν (cm-1) 2925, 1680, 1313, 1145, 734. MS (EI, 70 ev) m/z (%): 288 (M+), 244, 155, 105, 91, 77. HRMS-ESI (m/z): calcd for C16H16SO3, [M+Na]+ : 311.0712; found, 311.0718. 1-phenyl-2-tosylbutan-1-one (4va) 1 H NMR (400 MHz, CDCl3) δ 7.96 (d, J = 7.8 Hz, 2H), 7.65 (d, J = 7.9 Hz, 2H), 7.59 (t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.5 Hz, 2H), 7.32 7.27 (m, 2H), 5.00 (dd, J = 10.7, 3.5 Hz, 1H), 2.41 (s, 3H), 2.23 1.91 (m, 2H), 0.87 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 192.8, 145.3, 137. 5, 134.0, 133.5, 129.8, 129.5, 129.0, 128.8, 71. 5, 22.1 21.7, 11.5. IR (KBr) ν (cm-1) 2936, 1681, 1315, 1144, 754. MS (EI, 70 ev) m/z (%): 302 (M+), 274, 238, 146, 105, 77. HRMS-ESI (m/z): calcd for C17H18SO3, [M+Na]+ : 325.0869; found, 325.0875. 1-(thiophen-2-yl)-2-tosylethanone (4wa) 1 H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 3.8 Hz, 1H), 7.75 (t, J = 7.2 Hz, 3H), 7.33 (d, J = 8.0 Hz, 2H), 7.14 (dd, J = 12.2, 8.0 Hz, 1H), 4.61 (s, 2H), 2.43 (s, 3H). 13C NMR (100 MHz, CDCl3) δ 180.3, 145.5, 143.2, 136.4, 135.6, 135.3, 129.9, 128.7, 128.6, 64.7, 21.7. IR (KBr) ν (cm-1) 2933, 1653, 1385, 1149, 725. MS (EI, 70 ev) m/z (%): 280 (M+), 216, 155, 111, 108, 65. HRMS-ESI (m/z): calcd for C13H12S2O3, [M+Na]+ : 303.0120; found, 303.0127. 1-phenyl-2-(phenylsulfonyl)ethanone (4ab) 1 H NMR (400 MHz, CDCl3) δ 7.90 (dd, J = 12.1, 7.9 Hz, 4H), 7.68 7.57 (m, 2H), 7.53 (t, J = 7.6 Hz, 2H), 7.46 (t, J = 7.6 Hz, 2H), 4.74 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 188.0, 138.8, 135.8, 134.4, 134.2, 129.3, 129.2, 128.9, 128.6, 63.4. IR (KBr) ν (cm-1) 2929, 1679, 1318, 1153, 743. MS (EI, 70 ev) m/z (%): 260 (M+), 196, 141, 125, 105, 77. HRMS-ESI (m/z): calcd for C14H12SO3, [M+Na]+ : 283.0399; found, 283.0404. 5

2-((4-fluorophenyl)sulfonyl)-1-phenylethanone (4ac) 1 H NMR (400 MHz, CDCl 3 ) δ 7.93 7.82 (m, 4H), 7.66 7.55 (m, 1H), 7.47 (t, J = 7.6 Hz, 2H), 7.20 (t, J = 8.4 Hz, 2H), 4.74 (s, 2H). 13 C NMR (100MHz, CDCl 3 ) δ 188.1, 166.1(d, J = 256 Hz), 135.7, 134.7, 134.5, 131.7(d, J = 10 Hz), 129.2, 128.9, 116.5 (d, J = 23 Hz), 63.4. IR (KBr) ν (cm -1 ) 2927, 1679, 1326, 1152, 751. MS (EI, 70 ev) m/z (%): 278 (M+), 214, 159, 105, 95, 77. HRMS-ESI (m/z): calcd for C 14 H 11 FSO 3, [M+Na]+ : 301.0305; found, 301.0309. 2-((4-chlorophenyl)sulfonyl)-1-phenylethanone (4ad) 1 H NMR (400 MHz, CDCl 3 ) δ 7.93 (d, J = 7.9 Hz, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.63 (t, J = 7.3 Hz, 1H), 7.53 7.46 (m, 4H), 4.74 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.9, 141.1, 137.1, 135.6, 134.6, 130.2, 129.5, 129.3, 129.0, 63.3. IR (KBr) ν (cm -1 ) 2954, 1683, 1310, 1143, 748. MS (EI, 70 ev) m/z (%): 294(M+), 230, 175, 128, 105, 77. HRMS-ESI (m/z): calcd for C 14 H 11 ClSO 3, [M+Na]+ : 317.0010; found, 317.0012. 2-((4-bromophenyl)sulfonyl)-1-phenylethanone (4ae) 2 1 H NMR (400 MHz, CDCl 3 ) δ 7.93 (d, J = 7.9 Hz, 2H), 7.75 (d, J = 8.5 Hz, 2H), 7.68 (d, J = 8.3 Hz, 2H), 7.64 (t, J = 6.8 Hz, 1H), 7.49 (t, J = 7.6 Hz, 2H), 4.74 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.9, 137.7, 135.6, 134. 6, 132.5, 130.2, 129.8, 129.3, 129.0, 63.3. IR (KBr) ν (cm -1 ) 2923, 1652, 1316, 1244, 1149, 746. MS (EI, 70 ev) m/z (%): 338 (M+), 274, 174, 155, 105, 77. 2-((4-methoxyphenyl)sulfonyl)-1-phenylethanone (4af) 1 H NMR (400 MHz, CDCl 3 ) δ 7.88 7.81 (m, 2H), 7.74 7.68 (m, 2H), 7.56 7.49 (m, 1H), 7.38 (dd, J = 10.7, 4.8 Hz, 2H), 6.91 6.86 (m, 2H), 4.63 (s, 2H), 3.77 (s, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 188.3, 164.2, 135.8, 134.3, 130.9, 130.3, 129.3, 128.8, 114.4, 63.7, 55.7. IR (KBr) ν (cm -1 ) 3368, 2945,1680,1321,1027,748. MS (EI, 70 ev) m/z (%): 290 (M+), 226, 171, 124, 105, 77. HRMS-ESI (m/z): calcd for C 15 H 14 SO 4, [M+Na]+ : 313.0505; found, 313.0508. 1-phenyl-2-((4-(trifluoromethyl)phenyl)sulfonyl)ethanone (4ag) 1 H NMR (400 MHz, CDCl 3 ) δ 8.07 (dd, J = 19.0, 9.3 Hz, 2H), 7.93 (dd, J = 18.1, 10.8 Hz, 2H), 7.80 (t, J = 9.9 Hz, 2H), 7.63 (dd, J = 10.6, 4.3 Hz, 1H), 7.52 7.43 (m, 2H), 4.79 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.7,142.2, 135.8(d, J = 30 Hz), 135.5, 134.6, 129.4, 129.2, 129.0, 126.3(q, J = 3 Hz), 123.1(d, J =272 Hz), 63.1. IR (KBr) ν (cm -1 ) 2933, 1678, 1319, 1146, 746. MS (EI, 70 ev) m/z (%): 328 (M+), 264, 145, 105, 91, 77. HRMS-ESI (m/z): calcd for C 15 H 11 F 3 SO 3, [M+Na]+ : 351.0273; found, 351.0279. Ph O O S O Cl 2-((2-chlorophenyl)sulfonyl)-1-phenylethanone (4ah) 1 H NMR (400 MHz, CDCl 3 ) δ 8.08 8.03 (m, 1H), 7.94 (dd, J = 8.4, 1.2 Hz, 2H), 7.65 7.56 (m, 3H), 7.52 7.42 (m, 3H), 5.05 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 187.8, 136.5, 135.8, 135.1, 134.4, 132.7, 132.1, 131.9, 129.2, 128.9, 127.5, 61.0. IR (KBr) ν (cm -1 ) 2925, 1680, 1324, 1156, 752. MS (EI, 70 ev) m/z (%): 294 (M+), 230, 195, 128, 105, 77. HRMS-ESI (m/z): calcd for C 14 H 11 ClSO 3, [M+Na]+ : 317.0010; found, 317.0017. 2-(naphthalen-2-ylsulfonyl)-1-phenylethanone (4ai) 6

1 H NMR (400 MHz, CDCl 3 ) δ 8.46 (s, 1H), 8.02 7.84 (m, 6H), 7.69 7.57 (m, 3H), 7.51 7.41 (m, 2H), 4.81 (s, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 188.0, 135.8, 135.7, 135.6, 134.3, 132.0, 130.7, 129.6, 129.5, 129.5, 129.3, 128.8, 128.0, 127.7, 123.0, 63.6. IR (KBr) ν (cm -1 ) 2922, 1652, 1314, 1153, 749. MS (EI, 70 ev) m/z (%): 310 (M+), 246, 207, 144, 127, 105, 77. HRMS-ESI (m/z): calcd for C 18 H 14 SO 3, [M+Na]+ : 333.0556; found, 333.0562. 2-(methylsulfonyl)-1-phenylethanone (4aj) 3 1 H NMR (400 MHz, CDCl 3 ) δ 7.98 (d, J = 7.9 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.50 (t, J = 7.7 Hz, 2H), 4.61 (s, 2H), 3.12 (s, 3H). 13 C NMR (101 MHz, CDCl 3 ) δ 189.3, 135.7, 134.7, 129.2, 129.0, 61.2, 41.9. IR (KBr) ν (cm -1 ) 2924, 1652, 1244, 1056. MS (EI, 70 ev) m/z (%): 198 (M+), 105, 91, 77. 2-(ethylsulfonyl)-1-phenylethanone (4ak) 1 H NMR (400 MHz, CDCl 3 ) δ 8.01 (d, J = 7.8 Hz, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.51 (t, J = 7.7 Hz, 2H), 4.58 (s, 2H), 3.28 (q, J = 7.4 Hz, 2H), 1.45 (t, J = 7.4 Hz, 3H). 13 C NMR (100 MHz, CDCl 3 ) δ 189.3, 135. 8, 134.6, 129.3, 129.0, 58. 8, 48.3, 6.6. IR (KBr) ν (cm -1 ) 2941, 1680, 1315, 1126. MS (EI, 70 ev) m/z (%): 212 (M+), 147, 120, 105, 77. HRMS-ESI (m/z): calcd for C 10 H 12 SO 3, [M+Na]+ : 235.0399; found, 235.0404. Ph O O S O 2-(cyclopropylsulfonyl)-1-phenylethanone (4al) 1 H NMR (400 MHz, CDCl 3 ) δ 8.00 (d, J = 7.7 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.50 (t, J = 7.3 Hz, 2H), 4.64 (s, 2H), 2.80 2.66 (m, 1H), 1.24 (s, 2H), 1.06 (d, J = 7.3 Hz, 2H). 13 C NMR (100 MHz, CDCl 3 ) δ 188.9, 135.8, 134.5, 129.3, 129.0, 61.0, 30.9, 5.5. IR (KBr) ν (cm -1 ) 2948, 1682, 1322, 1142, 753. MS (EI, 70 ev) m/z (%): 224 (M+), 176, 145, 119, 105, 77. HRMS-ESI (m/z): calcd for C 11 H 12 SO 3, [M+Na]+ : 247.0399; found, 247.0406. A single crystal of product 3ta References 1. Anil. Kuma, M. K. Muthyala, Tetrahedron Lett. 2011, 52, 5368. 2. H. Loghmani-Khouzani, M. R. Poorheravi, M. M. M. Sadeghi, L. Caggiano, R. F.W. Jackson, Tetrahedron, 2008, 64, 7419. 3. N. Suryakiran, P. Prabhakar, K. Rajesh, V. Suresh, Y. Venkateswarlu, Journal of Molecular Catalysis A: Chemical. 2007, 207, 201. 4. C. Curti, M. Laget, A. O. Carle, A. Gellis, P. Vanelle, European Journal of Medicinal Chemistry, 2007, 42, 880. 7

NMR Spectra for all Compounds 3aa 8

3ja 10

3ka 12

3la 14

3ta 16

4aa 18

4ba 20

4ca 22

4da 24

4ea 26

4fa 28

4ga 30

4ha 32

4ia 34

4ma 36

4na 38

4oa 40

4pa 42

4qa 44

4ra 46

4sa 48

4ua 50

4va 52

4wa 54

4ab 56

4ac 58

4ad 60

4ae 62

4af 64

4ag 66

4ah 68

4ai 70

4aj 72

4ak 74

4al 76