SUPPORTING INFORMATION. Transition Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts

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1 S1 SUPPORTING INFORMATION Transition Metal-Free Arylations of In-Situ Generated Sulfenates with Diaryliodonium Salts Hao Yu, Zhen Li, and Carsten Bolm* Institute of Organic Chemistry, RWTH Aachen University Landoltweg 1, Aachen, Germany. Table of Content 1. General information S2 2. Experimental section S2 3. Characterization data S3 4. References S8 5. Copies of NMR spectra of the products S9

2 S2 1. General information Unless otherwise stated, all reagents were purchased from commercial suppliers and used without further purification. All the solvents were treated according to general methods. All product mixtures were analyzed by thin layer chromatography using aluminum foil backed silica TLC plates with a fluorescent indicator from Merck. UV-active compounds were detected with a UV lamp (λ = 254 nm). For flash column chromatography, silica gel was used as stationary phase. 1 H and 13 C NMR spectra were recorded either on a Varian V-NMRS 600, Varian V-NMRS 400 or Varian Mercury 300 in deuterated solvent. Chemical shifts (δ) are reported in parts per million (ppm), and spin-spin coupling constants (J) are given in Hz, while multiplicities are abbreviated by br s (broad singlet), s (singlet), d (doublet), t (triplet), q (quartet) and m (multiplet). The IR spectra were recorded with a PerkinElmer Spectrum 100 spectrometer with an attached UATR device Diamond KRS-5. All IR data were collected by attenuated total reflectance (ATR) and wave numbers ν are given in cm 1. Mass spectra were recorded with a Finnigan SSQ Finnigan 7000 spectrometer (EI, 70 ev). High resolution mass spectra (HRMS) were recorded on a Thermo Scientific LTQ Orbitrap XL spectrometer. β-sulfinyl esters 1 and diaryliodonium salts 2 were prepared according to the reported procedure. 1, 2 2. Experimental section O R S O KOH (50% aq) CO 2 t-bu + Ar 2 I TfO toluene/h 2 O R S Ar 1 2 rt, Ar, 24 h 3 In a 10 ml sealed tube under argon was successively added β-sulfinyl esters 1 (0.2 mmol, 1.0 equiv), diaryliodonium salts 2 (0.22 mmol, 1.1 equiv) and a mixture of toluene (1 ml) and H 2 O (1 ml). Then, a 50% aqueous KOH solution (4.0 mmol, 20.0 equiv) was added dropwise. The resulting turbid reaction mixture was stirred at room temperature for 24 h and then quenched by the addition of a 1M aqueous HCl solution (5 ml). After addition of water (5 ml) and extraction with CH 2 Cl 2 (3 10 ml), the combined organic layers were dried over MgSO 4, filtered and concentrated. The product was purified by column chromatography on silica gel to afford sulfoxides 3. Scale-up experiment: In a 50 ml sealed tube under argon was successively added tert-butyl 3-(p-tolylsulfinyl)propanoate 1a (268.2 mg, 1.0 mmol, 1.0 equiv), diphenyliodonium triflate 2a (473.0 mg, 1.1 mmol, 1.1 equiv) and a mixture of toluene (5 ml) and H 2 O (5 ml). Then. a 50% aqueous KOH solution (20.0 mmol, 20.0 equiv) was added dropwise. The resulting reaction mixture was stirred at room temperature for 24 h and then quenched by the addition of a 1M aqueous HCl solution (25 ml). After addition of water (25 ml) and extraction with CH 2 Cl 2 (3 25 ml), the combined organic layers were dried over MgSO 4, filtered and concentrated. The product was then purified by column chromatography on silica gel to afford sulfoxide 3aa.

3 S3 3. Characterization data 1-Methyl-4-(phenylsulfinyl)benzene (3aa) Prepared from 1a and 2a following the general procedure; white solid (42.3 mg, 98% yield). R f = 0.50 (pentane/etoac, 3:2). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), 7.50 (d, J = 8.2 Hz, 2H), (m, 3H), (m, 2H), 2.33 (s, 3H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 145.8, 142.4, 141.6, 130.8, 123.0, 129.2, 124.9, 124.6, IR (ATR): ν = 3051, 2923, 2857, 2321, 2171, 1726, 1590, 1471, 1443, 1392, 1305, 1259, 1150, 1085, 1042, 811, 748, 687. MS (CI): m/z = 433 ([2M+1] +, 52), 217 ([M+1] +, 100), 216 ([M] +, 33), 200 (66). Analytical data in agreement with those reported in the literature. 3 1-Methyl-3-(phenylsulfinyl)benzene (3ba) Prepared from 1b and 2a following the general procedure; light yellow oil (32.8 mg, 76% yield). R f = 0.65 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), (m, 5H), 7.32 (t, J = 7.6 Hz, 1H), 7.23 (d, J = 7.6 Hz, 1H), 2.37 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 145.6, 145.3, 139.6, 131.9, 131.0, 129.3, 129.1, 125.0, 124.8, 122.0, IR (ATR): ν = 3056, 2326, 2087, 1724, 1574, 1472, 1443, 1388, 1158, 1085, 1044, 1010, 823, 741, 692. MS (CI): m/z = 433 ([2M+1] +, 71), 217 ([M+1] +, 94), 216 ([M] +, 75), 200 (100). Analytical data in agreement with those reported in the literature. 4 1-Methyl-2-(phenylsulfinyl)benzene (3ca) Prepared from 1c and 2a following the general procedure; white solid (42.2 mg, 98% yield). R f = 0.50 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ 7.94 (dd, J = 1.2, 7.8 Hz, 1H), (m, 2H), (m, 5H), 7.16 (d, J = 7.4 Hz, 1H), 2.34 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 144.5, 142.9, 135.7, 131.1, , , 129.3, 127.1, 126.0, 124.7, IR (ATR): ν = 3052, 2922, 2854, 2326, 2086, 1991, 1578, 1445, 1146, 1060, 1024, 876, 766, 688. MS (CI): m/z = 433 ([2M+1] +, 100), 217 ([M+1] +, 98), 216 ([M] +, 24), 200 (92). Analytical data in agreement with those reported in the literature. 3 1-Ethyl-2-(phenylsulfinyl)benzene (3da) Prepared from 1d and 2a following the general procedure; white solid (38.2 mg, 83% yield). R f = 0.54 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (m, 5H), (m, 1H), (m, 1H), (m, 1H), 1.15 (t, J = 7.5 Hz, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 145.1, 142.5, 142.1, 131.3, 131.0, 129.3, 129.0, 127.2, 125.8, 125.0, 24.9, IR (ATR): ν = 3052, 2973, 2913, 2326, 2085, 1726, 1579, 1465, 1442, 1383, 1332, 1309, 1271, 1160, 1058, 1027, 798, 749, 687. MS (CI): m/z = 231 ([M+1] +, 100), 230 ([M] +, 4), 214 (24). HRMS (ESI): m/z calcd. for C 14 H 14 NaOS: found: Sulfinyldibenzene (3ea) Prepared from 1e and 2a following the general procedure; white solid (38.8 mg, 96% yield). R f = 0.50 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 4H), (m, 6H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 145.6, 131.0, 129.3, IR (ATR): ν = 3048, 2926, 2326, 2161, 2071, 1897, 1725, 1580, 1475, 1439, 1391, 1255, 1152, 1084, 1029, 996, 915, 847, 736, 688. MS (CI): m/z = 405 ([2M+1] +, 18), 203 ([M+1] +, 100), 202 ([M] +, 25), 186 (35). Analytical data in

4 S4 agreement with those reported in the literature. 3 1-Bromo-4-(phenylsulfinyl)benzene (3fa) Prepared from 1f and 2a following the general procedure; white solid (54.8 mg, 98% yield). R f = 0.58 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 2H), (m, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 145.1, 144.8, 132.5, 131.4, 129.5, 126.2, 125.5, IR (ATR): ν = 3078, 3046, 2923, 2855, 2659, 2325, 2175, 2062, 1985, 1910, 1726, 1568, 1471, 1447, 1384, 1271, 1163, 1086, 1065, 1034, 1001, 814, 753, 721, 693. MS (CI): m/z = 283 ([M+3] +, 100), 281 ([M+1] +, 100), 280 ([M] +, 9), 203 (27), 125 (18). Analytical data in agreement with those reported in the literature. 5 1-Chloro-4-(phenylsulfinyl)benzene (3ga) Prepared from 1g and 2a following the general procedure; light yellow oil (45.8 mg, 97% yield). R f = 0.54 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 5H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 145.2, 144.2, 137.2, 131.4, 129.6, 129.5, 126.1, IR (ATR): ν = 3054, 2920, 2325, 2084, 1577, 1473, 1443, 1388, 1086, 1044, 825, 783, 747, 690. MS (CI): m/z = 473 ([2M+1] +, 19), 237 ([M+1] +, 100), 236 ([M] +, 71), 220 (99), 217 (54), 216 (47). Analytical data in agreement with those reported in the literature. 3 1-(tert-Butyl)-4-(phenylsulfinyl)benzene (3ha) Prepared from 1h and 2a following the general procedure; white solid (41.2 mg, 80% yield). R f = 0.68 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 5H), 1.29 (s, 9H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 154.7, 145.6, 142.2, 130.9, 129.2, 126.4, 124.8, 124.7, 35.0, IR (ATR): ν = 3052, 2959, 2864, 2325, 2080, 1976, 1726, 1588, 1475, 1447, 1392, 1364, 1265, 1083, 1038, 922, 837, 747, 689. MS (CI): m/z = 259 ([M+1] +, 100), 258 ([M] +, 2), 118 (12), 77 (18). Analytical data in agreement with those reported in the literature. 6 1-Methoxy-4-(phenylsulfinyl)benzene (3ia) Prepared from 1i and 2a following the general procedure; white solid (44.1 mg, 95% yield). R f = 0.38 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 4H), (m, 3H), (m, 2H), 3.79 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 162.0, 145.7, 136.7, 130.7, 129.2, 127.2, 124.6, 114.8, IR (ATR): ν = 3048, 3012, 2934, 2839, 2325, 1904, 1725, 1588, 1495, 1443, 1411, 1300, 1258, 1183, 1086, 1024, 960, 829, 795, 752, 691. MS (CI): m/z = 233 ([M+1] +, 100), 232 ([M] +, 6), 184 (13), 155 (9), 77 (16). Analytical data in agreement with those reported in the literature. 3 1-Methoxy-2-(phenylsulfinyl)benzene (3ja) Prepared from 1j and 2a following the general procedure; white solid (45.5 mg, 98% yield). R f = 0.50 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ 7.90 (dd, J = 1.7, 7.8 Hz, 1H), (m, 2H), (m, 4H), (m, 1H), 6.84 (d, J = 8.3 Hz, 1H), 3.78 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 155.6, 145.5, 133.0, 132.2, 130.8, 128.9, 125.2, 124.5, 121.6, 111.0, IR (ATR): ν = 3070, 2929, 2840, 2325, 2077, 1725, 1583,

5 S5 1474, 1274, 1237, 1078, 1024, 760, 721, 688. MS (CI): m/z = 233 ([M+1] +, 100), 232 ([M] +, 6), 216 (12), 215 (15). Analytical data in agreement with those reported in the literature. 7 1, 2-Dimethoxy-4-(phenylsulfinyl)benzene (3ka) Prepared from 1k and 2a following the general procedure; white solid (48.2 mg, 92% yield). R f = 0.24 (pentane/etoac, 3:2). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), 7.18 (dd, J = 2.0, 8.3 Hz, 1H), 7.11 (d, J = 2.0 Hz, 1H), 6.87 (d, J = 8.3 Hz, 1H), 3.85 (s, 3H), 3.82 (s, 3H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 151.6, 150.0, 145.7, 136.8, 130.8, 129.2, 124.5, 118.8, 111.0, 107.1, 56.07, IR (ATR): ν = 3058, 3003, 2937, 2839, 2329, 2084, 1725, 1584, 1502, 1444, 1400, 1257, 1179, 1137, 1083, 1023, 852, 809, 753, 691. MS (CI): m/z = 263 ([M+1] +, 100), 262 ([M] +, 16), 246 (11). HRMS (ESI): m/z calcd. for C 14 H 14 NaO 3 S: found: (Phenylsulfinyl)naphthalene (3la) Prepared from 1l and 2a following the general procedure; white solid (41.3 mg, 82% yield). R f = 0.60 (pentane/etoac, 3:2). 1 H NMR (400 MHz, CDCl 3 ) δ 8.29 (s, 1H), (m, 3H), (m, 2H), (m, 6H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 145.4, 142.5, 134.3, 132.8, 131.1, 129.7, 129.3, 128.6, 128.0, 127.9, 127.3, 125.3, 125.0, IR (ATR): ν = 3051, 2924, 2326, 2080, 1775, 1722, 1580, 1499, 1475, 1439, 1343, 1301, 1154, 1078, 1039, 966, 866, 818, 744, 690. MS (CI): m/z = 253 ([M+1] +, 100), 252 ([M] +, 10), 236 (7). Analytical data in agreement with those reported in the literature. 3 2-(Phenylsulfinyl)pyridine (3ma) Prepared from 1m and 2a following the general procedure; white solid (39.8 mg, 98% yield). R f = 0.36 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 1H), (m, 1H), (m, 3H), (m, 3H), (m, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 165.8, 149.7, 144.0, 138.1, 131.1, 129.1, 124.9, 124.6, IR (ATR): ν = 3048, 2926, 2324, 2084, 1725, 1569, 1475, 1444, 1419, 1368, 1254, 1148, 1088, 1042, 993, 847, 751, 688. MS (CI): m/z = 204 ([M+1] +, 100), 203 ([M] +, 17), 186 (14). Analytical data in agreement with those reported in the literature. 3 2-(Phenylsulfinyl)thiophene (3na) Prepared from 1n and 2a following the general procedure; light yellow oil (39.5 mg, 95% yield). R f = 0.54 (pentane/etoac, 3:2). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 2H), (m, 2H), (m, 3H), (m, 1H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 148.0, 145.1, 132.3, 131.3, 131.1, 129.2, 127.2, IR (ATR): ν = 3070, 2328, 2084, 1581, 1474, 1442, 1401, 1222, 1083, 1041, 995, 848, 715, 692. MS (CI): m/z = 209 ([M+1] +, 100), 208 ([M] +, 4), 192 (19), 160 (13). Analytical data in agreement with those reported in the literature. 7 (Isopropylsulfinyl)benzene (3oa) Prepared from 1o and 2a following the general procedure; light yellow oil (14.2 mg, 42% yield). R f = 0.36 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), (m, 3H), (m, 1H), 1.22 (d, J = 6.8 Hz, 3H), 1.13 (d, J = 6.8 Hz, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 141.7, 130.9, 128.8, 125.0, 54.5, 15.9, IR (ATR): ν = 3058, 2925,

6 S6 2859, 2324, 2109, 1724, 1449, 1369, 1303, 1251, 1147, 1084, 1023, 844, 750, 694. MS (CI): m/z = 169 ([M+1] +, 100), 168 ([M] +, 3), 155 (13), 127 (24), 126 (11). Analytical data in agreement with those reported in the literature. 8 (Benzylsulfinyl)benzene (3pa) Prepared from 1p and 2a following the general procedure; white solid (30.2 mg, 70% yield). R f = 0.42 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 1H), (m, 2H), (m, 2H), (m, 3H), (m, 2H), 4.08 (d, J = 12.6 Hz, 1H), 3.99 (d, J = 12.6 Hz, 1H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 142.7, 131.2, 130.3, 129.1, 128.8, 128.4, 128.2, 124.4, MS (CI): m/z = 307 (100), 217 ([M+1] +, 97), 216 ([M] +, 4), 91 (51). Analytical data in agreement with those reported in the literature. 8 4, 4'-Sulfinylbis(methylbenzene) (3ab) Prepared from 1a and 2b following the general procedure; white solid (41.8 mg, 91% yield). R f = 0.61 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ 7.50 (d, J = 8.2 Hz, 4H), (m, 4H), 2.34 (s, 6H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 142.6, 141.4, 129.9, 124.8, IR (ATR): ν = 3030, 2922, 2863, 2324, 2074, 1914, 1726, 1593, 1489, 1450, 1394, 1152, 1085, 1036, 806, 760, 707. MS (CI): m/z = 231 ([M+1] +, 100), 230 ([M] +, 15), 214 (22), 182 (13), 139 (14), 91 (20), 65 (19). Analytical data in agreement with those reported in the literature. 9 1-(tert-Butyl)-4-(p-tolylsulfinyl)benzene (3ac) Prepared from 1a and 2c following the general procedure; white solid (52.8 mg, 97% yield). R f = 0.73 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 4H), (m, 2H), (m, 2H), 2.35 (s, 3H), 1.28 (s, 9H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 154.5, , , 141.4, 129.9, 126.3, 124.9, 124.7, 34.9, 31.2, IR (ATR): ν = 3031, 2964, 2925, 2866, 2323, 2079, 1915, 1726, 1592, 1487, 1456, 1391, 1365, 1264, 1150, 1081, 1041, 1010, 829, 807, 733, 702. MS (CI): m/z = 273 ([M+1] +, 100), 272 ([M] +, 10), 139 (30), 118 (19), 91 (30), 65 (19). HRMS (ESI): m/z calcd. for C 17 H 20 NaOS: found: Methoxy-4-(p-tolylsulfinyl)benzene (3ad) Prepared from 1a and 2d following the general procedure; white solid (42.3 mg, 86% yield). R f = 0.39 (pentane/etoac, 3:2). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), 7.22 (d, J = 8.1 Hz, 2H), (m, 2H), 3.77 (s, 3H), 2.33 (s, 3H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 161.8, 142.6, 141.2, 136.9, 129.9, 127.0, 124.7, 114.7, 55.4, IR (ATR): ν = 3016, 2925, 2848, 2299, 2165, 2058, 1914, 1726, 1590, 1491, 1454, 1405, 1304, 1249, 1172, 1084, 1032, 809, 710. MS (CI): m/z = 247 ([M+1] +, 4), 87 (27), 71 (100). Analytical data in agreement with those reported in the literature. 9 1-Fluoro-4-(p-tolylsulfinyl)benzene (3ae) Prepared from 1a and 2e following the general procedure; white solid (40.3 mg, 86% yield). R f = 0.54 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), 7.50 (d, J = 8.2 Hz, 2H), (m, 2H), (m, 2H), 2.36 (s, 3H).

7 S7 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ (d, J C-F = Hz), 142.2, 141.8, (d, J C-F = 3.0 Hz), 130.1, (d, J C-F = 9.0 Hz), 124.8, (d, J C-F = 22.7 Hz), IR (ATR): ν = 3036, 2974, 2922, 2299, 2168, 2089, 1902, 1725, 1586, 1488, 1398, 1221, 1151, 1088, 1043, 1013, 831, 806, 707. MS (CI): m/z = 469 ([2M+1] +, 39), 235 ([M+1] +, 72), 234 ([M] +, 41), 218 (100), 186 (18). Analytical data in agreement with those reported in the literature Chloro-4-(p-tolylsulfinyl)benzene (3af) Prepared from 1a and 2f following the general procedure; white solid (36.0 mg, 72% yield). R f = 0.61 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), 7.50 (d, J = 8.2 Hz, 2H), (m, 2H), 7.26 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 144.4, 142.1, 142.0, 137.0, 130.2, 129.5, 126.0, 124.9, IR (ATR): ν = 3047, 2920, 2854, 2166, 2087, 1912, 1725, 1572, 1472, 1390, 1084, 1044, 1010, 807, 738, 707. MS (CI): m/z = 253 ([M+3] +, 37), 251 ([M+1] +, 100), 250 ([M] +, 23), 234 (31), 202 (16). HRMS (ESI): m/z calcd. for C 13 H 11 ClNaOS: found: Bromo-4-(p-tolylsulfinyl)benzene (3ag) Prepared from 1a and 2g following the general procedure; white solid (38.8 mg, 66% yield). R f = 0.61 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ (m, 2H), (m, 4H), 7.25 (d, J = 8.1 Hz, 2H), 2.36 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 145.0, , , 132.4, 130.2, 126.1, 125.3, 124.9, IR (ATR): ν = 3034, 2962, 2923, 2857, 2323, 2079, 1913, 1726, 1567, 1469, 1384, 1260, 1150, 1086, 1043, 1007, 806, 720. MS (CI): m/z = 297 ([M+3] +, 100), 295 ([M+1] +, 92), 294 ([M] +, 26), 280 (34), 278 (35), 248 (19), 246 (21), 215 (15). Analytical data in agreement with those reported in the literature. 11 1, 4-Dimethyl-2-(p-tolylsulfinyl)benzene (3ah) Prepared from 1a and 2h following the general procedure; white solid (39.1 mg, 80% yield). R f = 0.52 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ 7.77 (s, 1H), 7.47 (d, J = 8.2 Hz, 2H), (m, 2H), 7.14 (d, J = 7.6 Hz, 1H), 7.03 (d, J = 7.6 Hz, 1H), 2.38 (s, 3H), 2.35 (s, 3H), 2.25 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 142.5, 141.6, 141.5, 137.0, 132.3, 131.6, 130.8, 130.0, 126.1, 124.6, 21.4, 21.1, IR (ATR): ν = 3034, 2921, 2855, 2087, 2036, 1727, 1593, 1489, 1452, 1374, 1308, 1144, 1080, 1057, 1021, 893, 811, 703. MS (CI): m/z = 489 ([2M+1] +, 100), 245 ([M+1] +, 69), 244 ([M] +, 7). HRMS (ESI): m/z calcd. for C 15 H 16 NaOS: found: , 3, 5-Trimethyl-2-(p-tolylsulfinyl)benzene (3ai) Prepared from 1a and 2h following the general procedure; colorless oil (25.8 mg, 50% yield). R f = 0.65 (pentane/etoac, 3:2). 1 H NMR (600 MHz, CDCl 3 ) δ 7.30 (d, J = 8.3 Hz, 2H), 7.22 (d, J = 8.2 Hz, 2H), 6.86 (s, 2H), 2.42 (s, 6H), 2.36 (s, 3H), 2.28 (s, 3H). 13 C{ 1 H} NMR (151 MHz, CDCl 3 ) δ 142.0, 141.1, 139.9, 139.7, 136.6, 130.7, 129.5, 124.5, 21.23, 21.16, IR (ATR): ν = 3022, 2923, 2862, 2163, 1907, 1725, 1599, 1570, 1488, 1451, 1379, 1294, 1251, 1150, 1081, 1036, 850, 808, 702. MS (CI): m/z = 517 ([2M+1] +, 6), 259 ([M+1] +, 100), 242 (8). HRMS (ESI): m/z calcd. for C 16 H 18 NaOS: found:

8 S8 1-(p-Tolylsulfinyl)naphthalene (3aj) Prepared from 1a and 2h following the general procedure; white solid (21.3 mg, 40% yield). R f = 0.48 (pentane/etoac, 3:2). 1 H NMR (400 MHz, CDCl 3 ) δ 8.22 (dd, J = 1.2, 7.3 Hz, 1H), (m, 1H), 7.94 (d, J = 8.2 Hz, 1H), (m, 1H), (m, 1H), (m, 4H), 7.17 (d, J = 8.0 Hz, 2H), 2.29 (s, 3H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 141.8, 141.6, 140.5, 133.7, 131.6, 130.0, 129.2, 128.8, 127.2, 126.6, 125.6, 125.5, 123.8, 122.5, IR (ATR): ν = 3054, 2922, 2855, 2322, 2079, 1727, 1591, 1499, 1455, 1375, 1260, 1078, 1039, 966, 862, 797, 769, 706, 663. MS (CI): m/z = 267 ([M+1] +, 100), 266 ([M] +, 4), 143 (11). Analytical data in agreement with those reported in the literature (p-Tolylsulfinyl)thiophene (3ak) Prepared from 1a and 2k following the general procedure; white solid (8.5 mg, 19% yield). R f = 0.53 (pentane/etoac, 1:1). 1 H NMR (400 MHz, CDCl 3 ) δ (m, 4H), 7.29 (d, J = 7.9 Hz, 2H), 7.04 (dd, J = 3.7, 5.0 Hz, 1H), 2.39 (s, 3H). 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 148.4, 142.0, 141.7, 132.0, 131.0, 130.0, 127.2, 124.4, IR (ATR): ν = 3071, 2923, 2330, 2087, 1910, 1593, 1490, 1446, 1400, 1220, 1044, 846, 809, 715. MS (EI): m/z = 223 ([M+1] +, 17), 222 ([M] +, 20), 206 (25), 175 (15), 174 (100), 173 (21). Analytical data in agreement with those reported in the literature References (1) Maitro, G.; Prestat, G.; Madec, D.; Poli, G. J. Org. Chem. 2006, 71, (2) (a) Reitti, M.; Villo, P.; Olofsson, B. Angew. Chem., Int. Ed. 2016, 55, (b) Chan, L.; McNally, A.; Toh, Q. Y.; Mendoza, A.; Gaunt, M. J. Chem. Sci. 2015, 6, (3) Jiang, H.; Jia, T.; Zhang, M.; Walsh, P. J. Org. Lett. 2016, 18, 972 (4) Izquierdo, F.; Chartoire, A.; Nolan, S.P. ACS Catal. 2013, 3, (5) Capozzi, M. A. M.; Centrone, C.; Fracchiolla, G.; Naso, F.; Cardellicchio, C. Eur. J. Org. Chem. 2011, (6) Jia, T.; Zhang, M.; Sagamanova, I. K.; Wang, C. Y.; Walsh, P. J. Org. Lett. 2015, 17, (7) Gelat, F.; Lohier, J.; Gaumont, A.; Perrioa, S. Adv. Synth. Catal. 2015, 357, (8) Jia, T.; Zhang, M.; Jiang, H.; Wang, C.Y.; Walsh, P. J. J. Am. Chem. Soc. 2015, 137, (9) Bernoud, E.; Le Duc, G.; Bantreil, X.; Prestat, G.; Madec, D.; Poli, G. Org. Lett. 2010, 12, 320. (10) Lenstra, D. C.; Vedovato, V.; Flegeau, E. F.; Maydom, J.; Willis, M. C. Org. Lett. 2016, 18, (11) Maitro, G.; Vogel, S.; Prestat, G.; Madec, D.; Poli, G. Org. Lett. 2006, 8, (12) Wang, B.; Liu, Y.; Lin, C.; Xu, Y.; Liu, Z.; Zhang, Y. Org. Lett. 2014, 16, (13) Richter, H.; Beckendorf, S.; Mancheño, O. G. Adv. Synth. Catal. 2011, 353, 295.

9 S9 5. Copies of NMR spectra for the products 1-Methyl-4-(phenylsulfinyl)benzene (3aa)

10 1-Methyl-3-(phenylsulfinyl)benzene (3ba) S10

11 1-Methyl-2-(phenylsulfinyl)benzene (3ca) S11

12 1-Ethyl-2-(phenylsulfinyl)benzene (3da) S12

13 Sulfinyldibenzene (3ea) S13

14 1-Bromo-4-(phenylsulfinyl)benzene (3fa) S14

15 1-Chloro-4-(phenylsulfinyl)benzene (3ga) S15

16 1-(tert-Butyl)-4-(phenylsulfinyl)benzene (3ha) S16

17 1-Methoxy-4-(phenylsulfinyl)benzene (3ia) S17

18 1-Methoxy-2-(phenylsulfinyl)benzene (3ja) S18

19 1, 2-Dimethoxy-4-(phenylsulfinyl)benzene (3ka) S19

20 1-(Phenylsulfinyl)naphthalene (3la) S20

21 2-(Phenylsulfinyl)pyridine (3ma) S21

22 2-(Phenylsulfinyl)thiophene (3na) S22

23 (Isopropylsulfinyl)benzene (3oa) S23

24 (Benzylsulfinyl)benzene (3pa) S24

25 4, 4'-Sulfinylbis(methylbenzene) (3ab) S25

26 1-(tert-Butyl)-4-(p-tolylsulfinyl)benzene (3ac) S26

27 1-Methoxy-4-(p-tolylsulfinyl)benzene (3ad) S27

28 1-Fluoro-4-(p-tolylsulfinyl)benzene (3ae) S28

29 1-Chloro-4-(p-tolylsulfinyl)benzene (3af) S29

30 1-Bromo-4-(p-tolylsulfinyl)benzene (3ag) S30

31 1, 4-Dimethyl-2-(p-tolylsulfinyl)benzene (3ah) S31

32 1, 3, 5-Trimethyl-2-(p-tolylsulfinyl)benzene (3ai) S32

33 1-(p-Tolylsulfinyl)naphthalene (3aj) S33

34 2-(p-Tolylsulfinyl)thiophene (3ak) S34