Supporting Information Palladium-Catalyzed Carbonylative Four-Component Synthesis of Thiochromenones: The Advantages of a Reagent Capsule Chaoren Shen, Anke Spannenberg, and Xiao-Feng Wu* anie_201600953_sm_miscellaneous_information.pdf
Contents 1. General Methods and Materials S2 2. General Procedure for the Preparation of Paraffin Wax Capsules containing Na2S 9H2O S2 3. General Procedure for the Preparation of the Substituted 1-Fluoro-2-Iodobenzenes. S2 4. General Procedure for the Synthesis of Thiochromenone. S2 5. Procedure for the Synthesis of 3-Iodo Derivatives of Thiochromone. S3 6. Characterization of Products S3 7. 1 H, 13 C, and 19 F NMR Spectral Data S11 8. Reference S44 S1
1. General Methods and Materials NMR spectra were recorded on Bruker Avance 300. Chemical shifts (ppm) are given relative to solvent: references for CDCl 3 were 7.26 ppm ( 1 H NMR) and 77.00 ppm ( 13 C NMR). Multiplets were assigned as s (singlet), d (doublet), t (triplet), dd (doublet of doublet), m (multiplet). All measurements were carried out at room temperature unless otherwise stated. Electron impact (EI) mass spectra were recorded on AMD 402 mass spectrometer (70 ev). High resolution mass spectra (HRMS) were recorded on Agilent 6210. The data are given as mass units per charge (m/z). The products were isolated from the reaction mixture by column chromatography on silica gel 60, 0.063-0.2 mm, 70-230 mesh (Merck). Paraffin wax (mp 65 C; ASTM D 87) and Na 2S 9H 2O (ACS reagent, 98.0%) were purchased from Sigma-Aldrich and used as received. 2. General Procedure for the Preparation of Paraffin Wax Capsules containing Na2S 9H2O Paraffin wax (mp 65 C, ASTM D 87) was placed in a beaker with a stir bar and heated to 75 C in a sand bath open to the air. Then molten, the volume of the molten colorless wax was approximately 100 ml. A room temperature glass rod with the tip (15 cm in length, 0.7 cm in diameter, Figure S1) was repeatedly dipped into the molten wax (to a depth of 4 cm) 2-3 times to develop a wax coating on the glass rod. The coated rod was allowed to cool to room temperature and the wax coating was removed from the glass rod to provide a hollow paraffin wax cone shell (Figure S2). The shell is charged with Na 2S 9H 2O (120 mg, 0.50 mmol). And then 4-5 drops of molten wax were dropped onto the Na 2S 9H 2O crystal to seal the open end of capsules. Once sealed, the extra wax was trimmed with a razor blade and dipped quickly into the molten wax to secure the seal. Figure S1. The glass rod for preparing paraffin wax capsules. Figure S2. Top view of a finished hollow wax shell. Figure S3 and S4. Top view and side view of a finished wax capsule. 3. General Procedure for the Preparation of the Substituted 1-Fluoro-2-Iodobenzenes. Substituted 1-fluoro-2-iodobenzenes were prepared from the corresponding substituted 1-bromo-2- fluorobenzene via Cu-catalyzed Finkerstein reaction aromatic Finkelstein reaction with NaI in dioxane reported by Buchwald et al. [1] 4. General Procedure for the Synthesis of Thiochromenone. A 12 ml Wheaton vial was charged with Pd(OAc)2 (4.5 mg, 4 mol%), tbu 3P HBF 4 (13.5 mg, 8 mol%), one paraffin wax capsule of Na 2S 9H 2O and a magnetic stirring bar. Then under argon, MeCN (2 ml) solution of 1- fluoro-2-iodobenzene (0.5 mmol), alkyne (0.5 mmol), triethylamine (1.5 mmol) were injected by syringe. The vial (or several vials) was placed in an alloy plate, which was transferred into a 300 ml autoclave of the 4560 series from Parr Instruments under Ar atmosphere. After flushing the autoclave three times with CO, a pressure of 5 bar CO was adjusted at ambient temperature. The reaction was performed for 24 h at 40 C (Note: avoid temperature rising too fast cause overheating above 45 C.). Then the temperature was elevated to 80 C for 12 h. After the reaction finished, the autoclave was cooled down to room temperature and the pressure was released carefully. The reaction mixture was diluted with acetone and passed through Celite. After evaporation of the S2
solvent the residue was adsorbed on silica gel and the crude product was purified by column chromatography using n-pentane/acoet as eluent. 5. The Procedure for the Synthesis of 3-Iodo Derivatives of Thiochromone. A mixture of 2-phenyl-4H-thiochromen-4-one (0.5 mmol), I 2 (0.6 mmol) and ammonium cerium nitrate (0.55 mmol) in MeCN (2 ml) was stirred at 55 C under Ar for 20 h. Then the mixture was slowly quenched with cold saturated Na 2S 2O 3 aqueous solution and extracted with CH 2Cl 2. The organic layer was washed with H 2O, dried with MgSO 4 and concentrated. The product was isolated by column chromatography on silica gel using n- pentane/acoet as eluent. 6. Characterization of Products. 2-Phenyl-4H-thiochromen-4-one (3a) 1 H NMR (300 MHz, CDCl 3): δ = 8.57 (1 H, ddd, J = 7.9, 1.5, 0.7 Hz), 7.74-7.48 (9 H, m). 13 C NMR (75 MHz, CDCl 3): δ = 181.16, 153.35, 138.02, 136.89, 131.92, 131.24, 131.14, 129.61, 128.93, 128.09, 127.29, 126.82, 123.77 GC-MS (EI, 70 ev): m/z (%) = 238 (100), 210 (99), 165 (17), 136 (58), 108 (40), 69 (14). 2-(o-Tolyl)-4H-thiochromen-4-one (3b) 1 H NMR (300 MHz, CDCl 3): δ = 8.59 (1H, dt, J = 7.8, 1.1 Hz), 7.65-7.54 (3H, m), 7.41-7.23 (5H, m), 2.39 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.50, 153.53, 138.41, 136.14, 135.73, 131.57, 130.98, 130.90, 129.82, 129.05, 128.68, 127.76, 126.28, 126.25, 126.08, 19.88. GC-MS (EI, 70 ev): m/z (%) = 252 (100), 235 (15), 223 (55), 210 (30), 191 (15), 175 (14), 147 (18), 136 (67), 115 (54), 108 (53), 89 (14), 69 (18). HRMS (EI): calcd. for C 16H 12OS [M] + 252.06034, found 252.06010. 2-(m-Tolyl)-4H-thiochromen-4-one (3c) 1 H NMR (300 MHz, CDCl 3): δ = 8.57 (1 H, ddd, J = 7.9, 1.6, 0.7 Hz), 7.71-7.48 (6H, m), 7.44-7.32 (2H, m), 2.46 (3 H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.88, 153.24, 139.16, 137.78, 136.55, 131.59, 131.55, 130.97, 129.16, 128.60, 127.72, 127.61, 126.47, 124.11, 123.32, 21.45. GC-MS (EI, 70 ev): m/z (%) = 252 (96), 224 (100), 136 (37), 115 (31), 108 (35) HRMS (EI): calcd. for C 16H 12OS [M] + 252.06034, found 252.06042 S3
2-(p-Tolyl)-4H-thiochromen-4-one (3d) 1 H NMR (300 MHz, CDCl 3): δ = 8.57 (1H, ddd, J = 7.9, 1.7, 0.7 Hz), 7.72-7.54 (6H, m), 7.36-7.31 (2H, m), 2.45 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.95, 153.16, 141.37, 137.75, 133.73, 131.56, 130.95, 130.01, 128.59, 127.72, 126.83, 126.49, 122.87, 21.43. GC-MS (EI, 70 ev): m/z (%) = 252 (100), 237 (7), 224 (82), 136 (64), 115 (27), 108 (39). HRMS (EI): calcd. for C 16H 12OS [M] + 252.06034, found 252.06010 2-([1,1'-Biphenyl]-4-yl)-4H-thiochromen-4-one (3e) 1 H NMR (300 MHz, CDCl 3): δ = 8.56 (1H, ddd, J = 7.9, 1.6, 0.7 Hz), 7.81-7.37 (13H, m). 13 C NMR (75 MHz, CDCl 3): δ = 180.86, 152.55, 143.76, 139.76, 137.63, 135.31, 131.61, 130.97, 128.99, 128.63, 128.10, 127.91, 127.79, 127.37, 127.14, 126.50, 123.19 GC-MS (EI, 70 ev): m/z (%) = 314 (100), 286 (68), 178 (48), 143 (21), 136 (32), 108 (27). HRMS (EI): calcd. for C 21H 14OS [M] + C 21H 14OS 314.07599, found 314.07585. 2-(4-Pentylphenyl)-4H-thiochromen-4-one (3f) 1 H NMR (300 MHz, CDCl 3): δ = 8.56 (1 H, dd, J = 8.0, 1.5 Hz), 7.70-7.60 (4H, m), 7.56 (1H, ddd, J = 8.3, 6.7, 1.8 Hz), 7.33 (2H, d, J = 8.2 Hz), 2.72-2.65 (2 H, m), 1.72-1.64 (2 H, m), 1.40-1.33 (4H, m), 0.96-0.90 (3H, m). 13 C NMR (75 MHz, CDCl 3): δ = 180.91, 153.12, 146.36, 137.74, 133.87, 131.50, 130.96, 129.33, 128.58, 127.67, 126.82, 126.46, 122.85, 35.74, 31.47, 30.91, 22.52, 14.01. GC-MS (EI, 70 ev): m/z (%) = 308 (100), 280 (7), 251 (48), 223 (71), 136 (24), 115 (37), 108 (17). HRMS (EI): calcd. for C 20H 20OS [M] + 308.12294, found 308.12279. 2-(4-Methoxyphenyl)-4H-thiochromen-4-one (3g) 1 H NMR (300 MHz, CDCl 3): δ = 8.63-8.57 (1H, m), 7.76-7.53 (6H, m), 7.10-7.03 (2H, m), 3.93 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.91, 161.86, 152.72, 137.62, 131.48, 130.92, 128.85, 128.56, 128.33, 127.65, 126.40, 122.21, 114.68, 55.50. GC-MS (EI, 70 ev): m/z (%) = 268 (100), 253 (5), 240 (37), 225 (35), 197 (15), 165 (8), 152 (8), 136 (34), 132 (32), 117 (16), 108 (36), 89 (32), 63 (21). HRMS (EI): calcd. for C 16H 12O 2S [M] + 268.05525, found 268.05505. S4
2-(4-(Trifluoromethoxy)phenyl)-4H-thiochromen-4-one (3h) 1 H NMR (300 MHz, CDCl 3): δ = 8.60 (1H, ddd, J = 7.9, 1.4, 0.8), 7.83-7.57 (6H, m), 7.44-7.39 (2H, m). 19 F NMR (282 MHz, CDCl 3): δ = -57.3 (s) 13 C NMR (75 MHz, CDCl 3): δ = 180.74, 151.31, 151.02, 137.34, 135.10, 131.83, 130.84, 128.70, 128.67, 128.03, 126.53, 123.88, 121.51, 120.37 (q, J = 256.5 Hz). GC-MS (EI, 70 ev): m/z (%) = 322 (100), 294 (75), 237 (8), 225 (23), 197 (16), 152 (8), 136 (91), 108 (54), 69 (46), 32 (33). HRMS (EI): calcd. for C 16H 9O 2F 3S [M] + 322.02699, found 322.02675. 2-(4-Fluorophenyl)-4H-thiochromen-4-one (3i) 1 H NMR (300 MHz, CDCl 3): δ = 8.54 (1H, dd, J = 7.5, 1.4 Hz), 7.72-7.62 (4H, m), 7.61-7.52 (1H, m), 7.24-7.16 (3H, m). 19 F NMR (282 MHz, CDCl 3): δ = -108.8 (m) 13 C NMR (75 MHz, CDCl 3): δ = 180.81, 164.33 (d, J = 250.2 Hz), 151.81, 137.45, 132.75 (d, J = 3.8 Hz), 131.74, 130.84, 129.00 (d, J = 8.3 Hz), 128.66, 127.92, 126.49, 123.48, 116.50 (d, J = 21.8 Hz) GC-MS (EI, 70 ev): m/z (%) = 256 (79), 228 (100), 196 (10), 183 (18), HRMS (EI): calcd. for C 15H 9OFS [M] + 256.03527, found 256.03488. 2-(4-(Trifluoromethyl)phenyl)-4H-thiochromen-4-one (3j) 1 H NMR (300 MHz, CDCl 3): δ = 8.60-8.54 (1H, m), 7.85-7.76 (4H, m), 7.71-7.55 (5H, m). 19 F NMR (282 MHz, CDCl 3): δ = -62.5 (s) 13 C NMR (75 MHz, CDCl 3): δ = 180.61, 151.12, 139.98, 137.26, 132.60 (q, J = 33.0 Hz), 131.89, 130.83, 128.85, 128.78, 128.71, 128.66, 128.10, 127.47, 126.54, 126.29 (q, J = 3.8 Hz), 124.41. GC-MS (EI, 70 ev): m/z (%) = 306 (68), 287 (7), 278 (100), 237 (8), 208 (8), 169 (9), 151 (12), 136 (28), 120 (9), 108 (33), 69 (22). HRMS (EI): calcd. for C 16H 9OF 3S [M] + 306.03207, found 306.03133. 2-(3-Fluorophenyl)-4H-thiochromen-4-one (3k) 1 H NMR (300 MHz, CDCl 3): δ = 8.61-8.56 (1H, m), 7.71-7.40 (8H, m). 19 F NMR (282 MHz, CDCl 3): δ = -110.6 (m) 13 C NMR (75 MHz, CDCl 3): δ = 180.78, 163.02 (d, J = 247.5 Hz), 151.46, 138.65 (d, J = 7.5 Hz), 137.40, 131.83, 131.02 (d, J = 8.3 Hz), 130.90, 128.70, 128.01, 126.55, 123.92, 122.76 (d, J = 3.8 Hz), 117.75 (d, J = 21.0 Hz), 114.20 (d, J = 23.3 Hz) GC-MS (EI, 70 ev): m/z (%) = 256 (72), 228 (100), 183 (17), 136 (30), 120 (13), 108 (31), 69 (15) S5
HRMS (EI): calcd. for C 15H 9OFS [M] + 256.03527, found 256.03536. 2-(2-Chlorophenyl)-4H-thiochromen-4-one (3l) 1 H NMR (300 MHz, CDCl 3): δ = 8.58 (1H, dt, J = 7.9, 1.3 Hz), 7.65-7.33 (8H, m). 13 C NMR (100 MHz, CDCl 3): δ = 180.43, 150.48, 138.18, 135.22, 132.61, 131.72, 131.13, 130.95, 130.72, 130.50, 128.74, 127.89, 127.26, 127.12, 126.36. GC-MS (EI, 70 ev): m/z (%) = 274 (38), 272 (99), 246 (33), 244 (85), 237 (30), 208 (21), 165 (25), 136 (100), 118 (15), 108 (63), 82 (15), 69 (25). HRMS (EI): calcd. for C 15H 9O 35 ClS [M] + 272.00571, found 272.00535; cacld. for C 15H 9O 37 ClS [M] + 274.00276, found 274.00243. 2-(3,4-Dichlorophenyl)-4H-thiochromen-4-one (3m) 1 H NMR (400 MHz, CDCl 3): δ = 8.63-8.59 (1H, m), 7.86 (1H, dd, J = 2.2, 0.4), 7.75-7.72 (2H, m), 7.69-7.57 (4H, m). 13 C NMR (100 MHz, CDCl 3): δ = 180.59, 150.14, 137.09, 136.39, 135.28, 133.79, 131.94, 131.31, 130.90, 130.80, 128.83, 128.72, 128.14, 126.55, 126.08, 123.98 GC-MS (EI, 70 ev): m/z (%) = 308 (55), 306 (80), 280 (65), 278 (93), 208 (24), 207 (22), 167 (43), 149 (85), 136 (100), 108 (65), 69 (40). HRMS (EI): calcd. for C 15H 8OCl 2S [M] + 305.96674, found 305.96725; calcd. for C 15H 8O 35 Cl 37 ClS [M] + 207.96379, found 307.96436. 2-Pentyl-4H-thiochromen-4-one (3n) 1 H NMR (300 MHz, CDCl 3): δ = 8.49 (1H, dt, J = 7.9, 1.2 Hz), 7.58-7.48 (3H, m), 6.86 (1H, s), 2.70-2.63 (2H, t, J = 10.2 Hz), 1.39-1.29 (6H, m), 0.92-0.87 (3H, m). 13 C NMR (75 MHz, CDCl 3): δ = 180.74, 156.64, 137.78, 131.33, 131.00, 128.55, 127.47, 126.24, 124.13, 37.47, 31.01, 29.51, 22.35, 13.94. GC-MS (EI, 70 ev): m/z (%) = 232 (21), 189 (11), 176 (100), 147 (19), 137 (26), 136 (62), 108 (17). HRMS (EI): calcd. for C 14H 16OS [M] + 232.09164, found 232.09153. 2-Octyl-4H-thiochromen-4-one (3o) 1 H NMR (300 MHz, CDCl 3): δ = 8.50 (1H, dt, J = 7.9, 1.2 Hz), 7.61-7.47 (3H, m), 6.87 (1H, s), 2.72 2.63 (2H, m), 1.37-1.22 (12H, m), 0.86 (3H, t, J = 6.9 Hz). 13 C NMR (75 MHz, CDCl 3): δ = 180.74, 156.64, 137.78, 131.32, 131.01, 130.92, 128.56, 127.47, 126.24, 124.13, 37.52, 31.83, 29.83, 29.25, 29.15, 28.90, 22.67, 14.13. GC-MS (EI, 70 ev): m/z (%) = 274 (20), 189 (59), 176 (100), 163 (15), 137 (24), 136 (43). HRMS (EI): calcd. for C 17H 22OS [M] + 274.13859, found 274.13837. S6
4H-Thiochromen-4-one (3p) 1 H NMR (300 MHz, CDCl 3): δ = 8.59-8.51 (1H, m), 7.82 (1H, d, J = 10.5 Hz), 7.62-7.59 (2H, m), 7.57-7.51 (1 H, m), 7.01 (1H, d, J = 10.5 Hz). 13 C NMR (75 MHz, CDCl 3): δ = 179.75, 137.90, 137.57, 132.34, 131.47, 128.72, 127.88, 126.72, 125.92. GC-MS (EI, 70 ev): m/z (%) = 162 (52), 134 (100), 108 (27), 69 (21). HRMS (EI): calcd. for C 9H 6OS [M] + 162.01339, found 162.01334. 6-Methyl-2-phenyl-4H-thiochromen-4-one (3s) 1 H NMR (300 MHz, CDCl 3): δ = 8.39-8.35 (1H, m), 7.72-7.67 (2H, m), 7.57 (1H, d, J = 8.2 Hz), 7.53-7.44 (4H, m), 7.24 (1H, s), 2.50 (3 H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.98, 153.03, 138.15, 136.72, 134.73, 133.07, 130.76, 130.74, 129.29, 128.36, 127.00, 126.40, 123.35, 21.38. GC-MS (EI, 70 ev): m/z (%) = 252 (100), 224 (76), 208 (5), 150 (27), 121 (35), 102 (8), 77 (10). 7-Methyl-2-phenyl-4H-thiochromen-4-one (3t) 1 H NMR (300 MHz, CDCl 3): δ = 8.43 (1H, d, J = 8.3 Hz), 7.71-7.65 (2H, m), 7.53-7.47 (3H, m), 7.45 (1H, dt, J = 1.6, 0.7 Hz), 7.36 (1H, ddd, J = 8.1, 1.6, 0.6 Hz), 7.21 (1H, s), 2.48 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.83, 152.68, 142.56, 137.85, 136.70, 130.75, 129.38, 129.28, 129.27, 128.73, 128.52, 126.99, 126.23, 123.48, 21.65. GC-MS (EI, 70 ev): m/z (%) = 252 (90), 224 (100), 223 (59), 150 (52), 121 (55), 112 (10), 78 (23). HRMS (EI): calcd. for C 16H 12OS 252.06034, found 252.06021. 8-Methyl-2-phenyl-4H-thiochromen-4-one (3u) 1 H NMR (300 MHz, CDCl 3): δ = 8.48-8.43 (1 H, m), 7.75-7.71 (2H, m), 7.57-7.42 (6H, m), 2.58 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 181.45, 152.16, 137.20, 136.94, 134.74, 132.82, 131.27, 130.77, 129.28, 127.12, 127.08, 126.49, 123.36, 19.65. GC-MS (EI, 70 ev): m/z (%) = 252 (81), 224 (100), 208 (5), 150 (28), 121 (70), 102 (10), 77 (18). 6-Chloro-2-phenyl-4H-thiochromen-4-one (3v) 1 H NMR (300 MHz, CDCl 3): δ = 8.54 (1 H, dd, J = 2.0, 0.8 Hz), 7.72-7.68 (3H, m), 7.63-7.61 (2H, m), 7.56-7.51 (4H, m) S7
13 C NMR (75 MHz, CDCl 3): δ = 179.71, 153.30, 136.29, 135.85, 134.38, 132.11, 132.05, 131.08, 129.40, 128.27, 127.99, 127.01, 123.29 GC-MS (EI, 70 ev): m/z (%) = 274 (37), 272 (100), 246 (34), 244 (71), 208 (22), 170 (64), 142 (44), 107 (21), 75 (19), 63 (25). HRMS (EI): calcd. for C 15H 9O 35 ClS [M] + 272.00571, found272.00551; calcd. for C 15H 9O 37 ClS [M] + 274.00276, found 274.00258. 7-Chloro-2-phenyl-4H-thiochromen-4-one (3w) 1 H NMR (300 MHz, CDCl 3): δ = 8.47 (1H, d, J = 8.7 Hz), 7.70-7.64 (3H, m), 7.55-7.47 (4H, m), 7.21 (1H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.02, 152.77, 139.03, 138.34, 136.19, 131.04, 130.22, 129.37, 129.31, 128.46, 126.96, 125.77, 123.59. 7-Fluoro-2-phenyl-4H-thiochromen-4-one (3x) 1 H NMR (300 MHz, CDCl 3): δ = 8.56 (1H, ddd, J = 9.0, 5.9, 0.4 Hz), 7.70-7.65 (2H, m), 7.54-7.49 (3H, m), 7.34 (1H, ddd, J = 8.5, 2.5, 0.4), 7.29-7.22 (1H, m, partially overlapping with the residual solvent peak of CDCl 3), 7.21 (1H, s). 13 C NMR (75 MHz, CDCl 3): δ = 179.92, 164.12 (d, J = 255 Hz), 152.73, 139.84 (d, J = 9.8 Hz), 136.22, 131.74 (d, J = 9.8 Hz), 131.03, 129.38, 127.63 (d. J = 2.3 Hz), 126.96, 123.51, 116.41 (d, J = 22.5 Hz), 112.37 (d, J = 24.8 Hz) 19 F NMR (282 MHz, CDCl 3): δ = -105.4 (m) 8-Fluoro-2-phenyl-4H-thiochromen-4-one (3y) 1 H NMR (300 MHz, CDCl 3): δ = 8.36 (1H, dd, J = 8.1, 1.2 Hz), 7.77-7.70 (2H, m), 7.57-7.49 (4H, m), 7.40 (1H, ddd, J = 9.4, 8.1, 1.3 Hz), 7.24 (1H, d, J = 0.7 Hz) 13 C NMR (75 MHz, CDCl 3): δ = 179.97 (d, J = 3.0 Hz), 157.92 (d, J = 246 Hz), 152.03, 136.54, 132.47, 131.09, 129.39, 127.85 (d, J = 7.5 Hz), 127.09, 124.20 (d, J = 3.0 Hz), 123.48, 117.14 (d, J = 21 Hz) 19 F NMR (282 MHz, CDCl 3): δ = -112.9 (m) GC-MS (EI, 70 ev): m/z (%) = 256 (97), 228 (100), 196 (8), 183 (18), 154 (66), 126 (59), 102 (15), 69 (16). 7-Methyl-2-(m-tolyl)-4H-thiochromen-4-one (3z) 1 H NMR (300 MHz, CDCl 3): δ = 8.49 (1 H, d, J = 8.2 Hz), 7.57-7.31 (7H, m), 2.54 (3H, s), 2.49 (3 H, s) 13 C NMR (75 MHz, CDCl 3): δ = 180.86, 152.91, 142.51, 139.15, 137.93, 136.65, 131.54, 129.33, 129.16, 128.75, 128.49, 127.63, 126.22, 124.12, 123.33, 21.66, 21.51 GC-MS (EI, 70 ev): m/z (%) = 266 (99), 238 (100), 221 (11), 150 (53), 121 (46) S8
HRMS (EI): calcd. for C 17H 14OS [M] + 266.07599, found 266.07594. 7-Chloro-2-(m-tolyl)-4H-thiochromen-4-one (3aa) 1 H NMR (300 MHz, CDCl 3): δ = 8.52 (1 H, d, J = 8.8 Hz), 7.70 (1H, dd, J = 1.9, 0.8 Hz), 7.57-7.51 (3H, m), 7.47-7.31 (3H, m), 2.49 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.10, 153.07, 139.31, 139.14, 138.31, 136.17, 131.87, 130.23, 129.34, 129.28, 128.44, 127.60, 125.79, 124.12, 123.46, 21.51. GC-MS (EI, 70 ev): m/z (%) = 288 (31), 286(85), 260 (38), 258 (100), 221 (16), 170 (52), 142 (27), 115 (36), 89 (12). HRMS (EI): calcd. for C 16H 11O 35 ClS [M] + 286.02136, found 286.02096; calcd. for C 16H 11O 37 ClS 288.01841, found 288.01831. 2-(3-Fluorophenyl)-6-methyl-4H-thiochromen-4-one (3ab) 1 H NMR (300 MHz, CDCl 3): δ = 8.35 (1H, dd, J = 1.7, 0.9 Hz), 7.56 (1H, d, J = 8.2 Hz), 7.49-7.44 (3H, m), 7.42-7.36 (1H, m), 7.24-7.17 (2H, m), 2.50 (3H, s). 13 C NMR (75 MHz, CDCl 3): δ = 180.83, 162.9 (d, J = 246.8 Hz), 151.36 (d, J = 2.3 Hz), 138.76 (d, J = 7.5 Hz), 138.38, 134.38, 133.24, 130.97 (d, J = 8.3 Hz), 130.69, 128.41, 126.42, 123.77, 122.73 (d, J = 3.0 Hz), 117.65 (d, J = 21 Hz), 114.17 (d, J = 23.3 Hz), 21.38. 19 F NMR (282 MHz, CDCl 3): δ = -110.7 (m) GC-MS (EI, 70 ev): m/z (%) = 270 (100), 242 (77), 241 (53), 150 (46), 121 (64), 78 (22). HRMS (EI): calcd. for 270.05092, found 270.05057. 6-Fluoro-2-(m-tolyl)-4H-thiochromen-4-one (3ac) 1 H NMR (300 MHz, CDCl 3): δ = 8.25 (1H, dd, J = 9.4, 2.9 Hz), 7.70 (1H, dd, J = 8.8, 4.8 Hz), 7.55-7.35 (6H, m), 2.48 (3H, s) 13 C NMR (75 MHz, CDCl 3): δ = 180.02, 162.2 (d, J = 248.2 Hz), 153.71, 139.29, 136.33, 133.13 (d, J = 2.3 Hz), 132.96 (d, J = 6.8 Hz), 131.82, 129.27, 128.64 (d, J = 7.5 Hz), 127.64, 124.15, 122.45, 120.45 (d, J = 24.0 Hz), 114.21 (d, J = 22.5 Hz), 21.50. 19 F NMR (282 MHz, CDCl 3): δ = -111.0 (m) GC-MS (EI, 70 ev): m/z (%) = 270 (100), 255 (13), 242 (64), 154 (59), 126 (48), 134 (9), 115 (27), 89 (8) HRMS (EI): calcd. for C 16H 11OFS [M] + 270.05092, found 270.05064. S9
7-Fluoro-2-(m-tolyl)-4H-thiochromen-4-one (3ad) 1 H NMR (300 MHz, CDCl 3): δ = 8.62 (1H, dd, J = 9.0, 5.9 Hz), 7.54 (2H, ddd, J = 6.5, 1.6, 0.7 Hz), 7.48-7.37 (3H, m), 7.35-7.28 (1H, m), 2.50 (3H, d, J = 0.7 Hz). 19 F NMR (282 MHz): δ = -105.5 (m) 13 C NMR (75 MHz, CDCl 3): δ = 179.94, 164.1 (d, J = 254.3 Hz), 152.95, 139.92 (d, J = 9.8 Hz), 136.19, 131.80, 131.71 (d, J = 8.3 Hz), 129.26, 127.66 (d, J = 2.3 Hz), 127.58, 124.09, 123.37, 116.36 (d, J = 21.8 Hz), 112.34 (d, J = 24.8 Hz), 21.49. GC-MS (EI, 70 ev): m/z (%) = 270 (74), 255 (8), 242 (100), 154 (33), 126 (27), 115 (25). HRMS (EI): calcd. for C 16H 11OFS [M] + 270.05092, found 270.05068. 7-Fluoro-2-(3-fluorophenyl)-4H-thiochromen-4-one (3ae) 1 H NMR (300 MHz, CDCl 3): δ = 8.63 (1H, dd, J = 9.0, 5.9 Hz), 7.59-7.52 (2H, m), 7.48-7.40 (2H, m), 7.38-7.27 (3H, m). 19 F NMR (282 MHz): δ = -105.0 (m), -110.4 (m) 13 C NMR (75 MHz, CDCl 3): δ = 179.77, 164.2 (d, J = 254.3 Hz), 163.0 (d, J = 247.5 Hz), 151.08, 139.51 (d, J = 9.8 Hz), 138.10 (d, J = 7.5 Hz), 131.82 (d, J = 9.8 Hz), 131.10 (d, J = 7.5 Hz), 127.60, 123.99, 122.71 (d, J = 3.0 Hz), 117.93 (d, J = 21.0 Hz), 116.62 (d, J = 22.5 Hz), 114.17 (d, J = 23.3 Hz), 112.43 (d, J = 24.8 Hz). GC-MS (EI, 70 ev): m/z (%) = 274 (78), 246 (100), 214 (9), 201 (15), 154 (50), 126 (36). HRMS (EI): calcd. for C 15H 6OF 2S [M] + 274.02584, found 274.02565. Bis(2-phenylvinyl)sulfide (mixture of cis,cis-diastereomer and cis,trans-diastereomer) 1 H NMR (300 MHz, CDCl 3): δ = 7.59-7.52 (4 H, m), 7.49-7.37 (8 H, m), 7.36-7.28 (4 H, m), 6.90 (1H, d, J = 15.6 Hz, C=CH cis, trans), 6.74 (1H, d, J = 15.6 Hz), 6.67 (1 H, d, J = 10.7 Hz, C=CH cis, cis), 6.61 (1H, d, J = 10.8 Hz, C=CH cis, cis), 6.54 (1H, d, J = 10.8 Hz, C=CH cis, trans), 6.44 (1H, d, J = 10.8 Hz, C=CH cis, cis). 13 C NMR (75 MHz, CDCl 3): δ = 136.46 (cis,cis-diastereomer), 136.34 (cis,trans-diastereomer), 136.27 (cis,trans-diastereomer), 129.80 (cis,trans-diastereomer), 128.81 (cis,cis-diastereomer), 128.76 (cis,cisdiastereomer), 128.44 (cis,trans-diastereomer), 128.38 (cis,trans-diastereomer),, 127.57 (cis,trans-diastereomer), 127.47 (cis,trans-diastereomer), 127.23 (cis,cis-diastereomer), 126.87 (cis,cis-diastereomer), 126.08 (cis,cisdiastereomer), 125.92 (cis,trans-diastereomer), 123.94 (cis,trans-diastereomer), 123.84 (cis,trans-diastereomer) GC-MS (EI, 70 ev): m/z (%) = 238 (100), 237 (26), 205 (42), 204 (22), 178 (18), 147 (24), 128 (34), 115 (75), 91 (72), 77 (68). HRMS (EI): calcd. for C 16H 14S [M] + 238.08107, found 238.08044. 3-Iodo-2-phenyl-4H-thiochromen-4-one (4) 1 H NMR (300 MHz, CDCl 3): δ = 8.62 (1H, d, J = 7.6 Hz), 7.69-7.58 (3H, m), 7.54-7.49 (3H, m), 7.46-7.40 (2H, m). 13 C NMR (75 MHz, CDCl 3): δ = 176.34, 154.22, 140.78, 137.38, 131.98, 130.13, 130.11, 128.75, 128.56, 128.49, 127.37, 125.15, 103.23 GC-MS (EI, 70 ev): m/z (%) = 364 (100), 336 (12), 237 (51), 208 (62), 165 (69), 136 (13), 89 (19). S10
5. 1 H, 13 C, and 19 F NMR Spectral Data S11
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8. Reference [1] A.Klapars, S. L. Buchwald, J. Am. Chem. Soc. 2002, 124, 14844-14845. S44