Supporting Information Cobalt(II)-Catalyzed Acyloxylation of C- Bonds in Aromatic Amides with Carboxylic Acids Rina Ueno, Satoko atsui, and aoto Chatani* Department of Applied Chemistry, Faculty of Engineering, saka University, Suita, saka 565-0871, Japan chatani@chem.eng.osaka-u.ac.jp Contents I. General Information S2 II. Materials S2 III. Synthesis of Starting Materials S2-3 IV. General Procedure for the Direct Alkylation S3 V. Spectroscopic Data S3-16 VI. Deuterium Labeling Experiments S16-17 VII. Copies of 1 and 13 C MR Spectra S18-70 S1
I. General Information 1 MR and 13 C MR spectra were recorded on a JEL ECS-400 spectrometer in CDCl 3 with tetramethylsilane as the internal standard. Data are reported as follows: chemical shifts in ppm ( ), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, c= complex), coupling constant (z), and integration. Infrared spectra (IR) were obtained using a JASC FT/IR-4200 spectrometer; absorptions are reported in reciprocal centimeters with the following relative intensities: s (strong), m (medium), or w (weak). Mass spectra and high resolution mass spectra (RMS) were obtained using a JEL JMS-700 spectrometer. Column chromatography was performed with Si 2 (Silicycle SiliaFlash F60 (230-400 mesh)). II. Materials 1,2-Dichloroethane (CAS 107-06-2), Cyclohexanecarboxylic Acid (CAS 98-89-5), Acetic Acid (CAS 64-19-7), were purchased from acalai Tesque. Co(acac) 2 (CAS 14024-48-7), o-toluic acid (CAS 118-90-1), 2,6-Dimethylbenzoic Acid(CAS 632-46-2), Benzoic Acid(CAS 65-85-0), Biphenyl- 2-carboxylic Acid (CAS 947-84-2), 4-Chloro-2-methylbenzoic Acid (CAS 7499-07-2), 4-Fluoro-2- methylbenzoic Acid (CAS 321-21-1), 4-Methoxy-2-methylbenzoic Acid (CAS 6245-57-4), 2-Bromo- 4-methylbenzoic Acid (CAS 7697-27-0), 2,6-Difluorobenzoic Acid (CAS 385-00-2), Pivalic Acid (CAS 75-98-9), o-ansic Acid (CAS 579-75-9), 2-(Trifluoromethyl)benzoic Acid (CAS 433-97-6), 3- Methoxy-2-methylbenzoic Acid (CAS 55289-06-0) and 8-Aminoquinoline (CAS 578-66-5) were purchased from Tokyo Chemical Industry Co. Ag 2 C 3 (CAS 534-16-7) was purchased from Wako Pure Chemical Industries, Ltd. III. Synthesis of Starting Materials All amides bearing an 8-aminoquinoline moiety were prepared by reacting the corresponding acid or acid chloride with 8-aminoquinoline. 1 General Procedure for the Preparation of Starting Amides. (1) Synthesis of amides from carboxylic acids. To a stirred solution of a carboxylic acid (15 mmol) and DMF (5 drops) in C 2 Cl 2 (10 ml), (CCl) 2 (1.5 ml, 18 mmol) was added dropwise. The solution was magnetically stirred at room temperature for 2 h. The solvent was then removed by evaporation under reduced pressure, and the resulting residue was dissolved in C 2 Cl 2 (15 ml). After cooling the reaction mixture to 0 C, a solution of 8- Aminoquinoline (17 mmol) and triethylamine (30 mmol) in 10 ml of the same solvent was added dropwise. The resulting mixture was allowed to warm to rt and stirred overnight. The solution 1 (a) Ano, Y.; Tobisu, M.; Chatani,. rg. Lett. 2012, 14, 354. (b) Aihara, Y.; Chatani,. Chem. Sci. 2012, 4, 664. (c) Shibata, K.; Chatani,. rg. Lett. 2014, 16, 5148. S2
containing the crude product was washed with saturated aqueous ac 3 (20 ml), and C 2 Cl 2 (3x20 ml). The combined organic phase was washed with 1 M Cl aq. (20 ml).the organic phase was dried over anhydrous a 2 S 4 and the solvent removed by evaporation. The resulting crude amide was purified by flash chromatography on silica gel (eluent: hexane/etac = 5/1). IV. Synthesis of Acyloxylation Products. (1) General Procedure for the Acyloxylation of C- Bonds in Aromatic Amides with Carboxylic Acids To a 5 ml screw-capped vial, 2-methyl--(8-quinolinyl)benzamide (1a) (39.3 mg, 0.15 mmol), Co(acac) 2 (3.9 mg, 0.015 mmol), 2,6-dimethyl benzoic acid (2a) (33.8 mg, 0.225 mmol), Ag 2 C 3 (55.2 mg, 0.2 mmol) and DCE (0.5 ml) were added in air. The mixture was stirred for 3 h at 100 C. The mixture was washed with saturated aqueous ac 3 (10 ml) and brine (10 ml). The organic phase was concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluent: hexane/etac= 10/1) to afford the alkylation product 3aa (49.4 mg, 80%) as a white solid. (2) A gram scale reaction To a 20 ml screw-capped vial, 2-methyl--(8-quinolinyl)benzamide (1a) (262.2 mg, 1.00 mmol), Co(acac) 2 (25.9 mg, 0.1 mmol), 2,6-dimethyl benzoic acid (2a) (225.8 mg, 1.50 mmol), Ag 2 C 3 (368.5 mg, 1.34 mmol) and DCE (3.3 ml) were added in air. The mixture was stirred for 3 h at 100 C. The mixture was washed with saturated aqueous ac 3 (15 ml) and brine (15 ml). The organic phase was concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluent: hexane/etac= 10/1) to afford the alkylation product 3aa (349.6 mg, 85%) as a white solid. V. Spectroscopic Data 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3aa) 49.4 mg, 80% yield. White solid. Mp = 145.8-146.1 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : 2.25 (s, 6), 2.50 (s, 3), 6.89 (d, J = 7.8 z, 2), 7.09 (t, J = 7.6 z, 1), 7.17-7.25 (c, 2), 7.39-7.45 (c, 2), 7.53-7.59 (c, 2), 8.14 (dd, J = 8.2, 1.8 z, 1), 8.71 (dd, J = 4.1, 1.4 z, 1), 8.92 (dd, J = 6.9, 2.3 z, 1), 10.14 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.52, 19.83, 116.99, 120.28, 121.81, 122.26, 127.38, 127.67, 128.00, 128.41, 129.83, 130.27, 131.65, S3
132.59, 134.41, 135.65, 136.32, 137.48, 138.48, 147.46, 148.49, 165.07, 168.62. IR (ATR): 3337 w, 3018 w, 2978 w, 1749 m, 1681 m, 1524 s, 1484 m, 1424 w, 1386 w, 1327 w, 1263 w, 1217 s, 1103 w, 1054 w, 772 s. MS, m/z (relative intensity, %): 410 (M +, 13), 134 (10), 133 (100), 105 (22). RMS Calcd for C 26 22 2 3 410.1630, found 410.1632. 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2-methyl benzoate (3ab) 38.1 mg, 64% yield. White solid. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.48 (s, 3), 2.53 (s, 3), 6.93 (t, J = 7.6 z, 1), 7.08 (d, J = 7.8 z, 1), 7.18-7.27 (c, 2), 7.39-7.45 (c, 2), 7.48-7.55 (c, 2), 7.98 (dd, J = 8.0, 1.1 z, 1), 8.12 (dd, J = 8.3, 1.8 z, 1), 8.73 (dd, J = 4.1, 1.8 z, 1), 8.88 (dd, J = 6.9, 2.3 z, 1), 10.12 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.64, 21.75, 116.91, 120.59, 121.71, 122.13, 125.65, 127.40, 127.97, 128.03, 128.24, 130.22, 131.18, 131.42, 131.68, 132.65, 134.39, 136.28, 137.70, 138.51, 141.44, 147.82, 148.33, 165.15, 165.81. RMS Calcd for C 25 20 2 396.1474, found 396.1476. This compound has been reported previously. 2 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl benzoate (3ac) 19.2 mg, 33% yield. White solid. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.51 (s, 3), 7.17-7.26 (c, 3), 7.38-7.45 (c, 3), 7.48-7.53 (c, 2), 8.01 (dd, J = 8.3, 1.4 z, 2), 8.11 (dd, J = 8.3, 1.8 z, 1), 8.74 (dd, J = 4.4, 1.6 z, 1), 8.85 (dd, J = 6.4, 2.3 z, 1), 10.11 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.69, 116.89, 120.44, 121.70, 122.10, 127.39, 127.96, 128.29, 129.09, 130.22, 130.29, 130.86, 133.50, 134.36, 136.29, 137.82, 138.49, 147.82, 148.35, 164.97, 165.14. IR (ATR): 3348 w, 3025 w, 2933 w, 1677 m, 1582 w, 1520 s, 1481 m, 1385 w, 1325 w, 1269 m, 1096 w, 1044 w, 907 w, 825 w, 791 w, 755 w, 699 w. MS, m/z (relative intensity, %): 396 (M +, 2 Wang, F.; u, Q.; Shu, C.; Lin, Z.; Win, D.; Shi, T.; Zhang, W. rg. Lett. 2017, 19, 3636. S4
45), 305 (26), 254 (12), 253 (70), 252 (100), 175 (21), 147 (13), 145 (11), 144 (78), 135 (11), 91 (14). RMS Calcd for C 24 18 2 3 382.1317, found 382.1319. This compound has been reported previously. 2 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl [1,1'-biphenyl]-2-carboxylate (3ad) 52.5 mg, 76% yield. White solid. Mp = 128.3-128.8 C. R f 0.14 (hexane/etac = 5/1). 1 MR (CDCl 3, 400 Mz) : 2.46 (s, 3), 6.82 (d, J = 7.8 z, 1), 7.04 (td, J = 7.7, 1.2 z, 1), 7.13 (d, J = 7.8 z, 1), 7.32-7.23 (m, 7), 7.37 (td, J = 7.6, 1.2 z, 1), 7.42 (q, J = 4.1 z, 1), 7.58-7.52 (m, 2), 7.67 (dd, J = 7.8, 1.4 z, 1), 8.15 (dd, J = 8.5, 1.6 z, 1), 8.72 (q, J = 2.0 z, 1), 8.91 (dd, J = 6.9, 2.3 z, 1), 10.03 (s, 1). 13 C MR (CDCl 3, 101 Mz) : 19.62, 116.86, 119.94, 121.76, 122.14, 127.01, 127.42, 127.98, 128.12, 128.23, 128.62, 129.55, 130.17, 130.25, 130.77, 130.98, 131.67, 134.45, 136.29 (two overlapping peaks), 137.44, 138.52, 140.96, 143.15, 147.65, 148.42, 164.94, 166.82. IR (ATR): 3334 w, 3014 w, 2968 w, 2925 w, 2850 w, 2359 w, 1740 s, 1679 w, 1523 m, 1483 w, 1457 w, 1423 w, 1368 m, 1218 s, 1040 s, 772 s. MS, m/z (relative intensity, %): 380 (M +, 22), 238 (18), 237 (100), 236 (59), 179 (12), 159 (19), 145 (13), 144 (91), 131 (17), 91 (12). RMS Calcd for C 30 22 2 3 458.1630, found 458.1637. 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 4-fluoro-2-methylbenzoate (3ae) 35.6 mg, 57% yield. White solid. Mp = 114.8-115.4 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.48 (s, 3), 2.53 (s, 3), 6.58 (td, J = 8.4, 2.4 z, 1), 6.77 (dd, J = 9.6, 2.8 z, 1), 7.17-7.26 (c, 2), 7.41-7.45 (c, 2), 7.50-7.55 (c, 2), 8.01 (dd, J = 8.7, 6.0 z, 1), 8.13 (dd, J = 8.3, 1.4 z, 1), 8.73 (dd, J = 4.4, 1.6 z, 1), 8.87 (dd, J = 6.4, 2.8 z, 1), 10.10 (s, 1). 13 C MR (CDCl 3, 101 Mz) : 19.60, 21.98, 112.58, 112.79, 116.82, 118.32, 118.53, 120.52, 121.71, 122.14, 124.07, 127.38, 127.94, 128.29, 130.21, 131.04, 134.08, 134.17, 134.30, 136.31, 137.73, S5
138.42, 145.15, 145.23, 148.0 (d, J = 244.1 z), 163.66, 164.73, 165.04. IR (ATR): 3340 w, 3059 w, 3025 w, 2926 w, 2860 w, 2359 w, 1738 s, 1676 s, 1607 w, 1581 w, 1521 s, 1482 s, 1461 m, 1424 m, 1384 m, 1325 m, 1262 w, 1217 s, 1111 m, 1051 m, 960 w, 897 w, 826 m, 761 m, 682 w. MS, m/z (relative intensity, %): 384 (M +, 21), 241 (24), 240 (52), 163 (16), 145 (14), 144 (100), 135 (14), 91 (13). RMS Calcd for C 25 19 F 2 3 414.1380, found 414.1381. 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 4-chloro-2-methylbenzoate (3af) The compound 3af was prepared according to general procedure (the amount of Co(acac) 2 was increased to 20 mol%). 35.0 mg, 54% yield. White solid. Mp = 115.2-115.7 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.45 (s, 3), 2.53 (s, 3), 6.88 (dd, J = 8.5, 2.1 z, 1), 7.06 (d, J = 1.8 z, 1), 7.17-7.26 (c, 1), 7.41-7.45 (c, 2), 7.51-7.56 (c, 2), 7.91 (d, J = 8.3 z, 1), 8.14 (dd, J = 8.3, 1.4 z, 1), 8.72 (dd, J = 4.1, 1.8 z, 1), 8.86 (dd, J = 6.0, 3.2 z, 1), 10.08 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.66, 21.69, 76.85, 77.16, 77.37, 77.47, 116.85, 120.51, 121.77, 122.22, 125.89, 126.40, 127.43, 127.98, 128.41, 130.27, 131.05, 131.60, 132.82, 134.31, 136.35, 137.80, 138.46, 138.75, 143.49, 147.68, 148.33, 164.94, 165.03. IR (ATR): 3342 w, 3016 w, 2968 w, 2360 w, 2333 w, 1739 s, 1677 m, 1595 w, 1522 s, 1482 m, 1425 m, 1382 m, 1325 m, 1218 s, 1104 s, 1051 w, 897 w, 827 w, 769 m, 680 w. MS, m/z (relative intensity, %): 444 (M +, 6), 303 (10), 302 (18), 301 (12), 300 (17), 145 (13), 144 (100), 91 (12). RMS Calcd for C 25 19 Cl 2 3 430.1084, found 430.1079. 2-methyl-4-phenethyl-3-(quinolin-8-ylcarbamoyl)phenyl acetate (3ag) 49.7 mg, 77% yield. White solid. Mp = 103.3-103.9 C. R f 0.14 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : 2.49 (s, 3), 2.52 (s, 3), 3.73 (s, 3), 6.42 (dd, J = 8.7, 2.7 z, 1), 6.57 (d, J = 2.7 z, 1), 7.20 (dd, J = 12.1, 8.0 z, 2), 7.40-7.44 (c, 2), 7.49-7.55 (c, 2), 8.01 (d, J = 8.7 S6
z, 1), 8.13 (dd, J = 8.2, 1.8 z, 1), 8.75 (dd, J = 4.4, 1.6 z, 1), 8.89 (dd, J = 6.9, 2.3 z, 1), 10.12 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.64, 22.40, 55.34, 110.88, 116.82, 116.88, 120.06, 120.73, 121.69, 122.04, 127.39, 127.94, 128.04, 130.15, 131.19, 133.95, 134.43, 136.24, 137.65, 138.50, 144.52, 147.91, 148.29, 162.78, 165.23, 165.28. IR (ATR): 3334 w, 3012 w, 2969 w, 2924 w, 2360 w, 2341 w, 1739 s, 1678 w, 1605 w, 1523 m, 1483 w, 1425 w, 1368 m, 1325 w, 1218 s, 1122 w, 1036 w, 898 w, 827 w, 770 s, 685 w. MS, m/z (relative intensity, %): 424 (M +, 13), 281 (21), 239 (41), 238 (52), 161 (14), 145 (13), 144 (100), 91 (16). RMS Calcd for C 26 22 2 4 426.1580, found 426.1581. 2-methyl-6-phenethyl--(quinolin-8-yl)-3-(trifluoromethyl)benzamide (3ah) The compound 3ah was prepared according to general procedure (the amount of Co(acac) 2 was increased to 20 mol%). 51.5 mg, 72% yield. White solid. Mp = 118.8-119.5 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.33 (s, 3), 2.53 (s, 3), 6.91 (t, J = 7.8 z, 1), 7.17-7.27 (c, 3), 7.38-7.45 (c, 3), 7.51-7.58 (c, 2), 8.13 (dd, J = 8.2, 1.8 z, 1), 8.72 (dd, J = 4.1, 1.8 z, 1), 8.92 (dd, J = 7.3, 1.8 z, 1), 10.12 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.63, 23.78, 116.97, 120.40, 121.75, 122.20, 123.68, 126.70, 127.40, 127.99, 128.53, 128.66, 130.32, 131.03, 132.54, 133.65, 134.42, 136.30, 137.61, 138.51, 139.78, 147.60, 148.45, 164.93, 165.49. IR (ATR): 3337 w, 3009 w, 2969 w, 2925 m, 2850 w, 1744 s, 1678 m, 1523 s, 1482 m, 1424 m, 1380 m, 1326 w, 1266 w, 1220 s, 1174 w, 1122 w, 1100 m, 1053 w, 753 m. MS, m/z (relative intensity, %): 434 (M +, 9), 291 (15), 290 (21), 213 (12), 185 (19), 145 (12), 144 (100), 91 (21). RMS Calcd for C 25 19 Br 2 3 474.0579, found 474.0575. 3,6-dimethyl-2-phenethyl--(quinolin-8-yl)benzamide (3ai) 49.0 mg, 78% yield. White solid. Mp = 99.6-100.4 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, S7
400 Mz) : δ 2.52 (s, 3), 6.77 (t, J = 8.2 z, 2), 7.24 (t, J = 7.3 z, 2), 7.28-7.32 (c, 1), 7.39-7.45 (c, 2), 7.53-7.60 (c, 2), 8.14 (dd, J = 8.2, 1.8 z, 1), 8.72 (dd, J = 4.4, 1.6 z, 1), 8.92 (dd, J = 6.9, 1.8 z, 1), 10.09 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.60, 110.12 (t, J = 66.0 z), 112.07, (d, J = 103.1 z).06, 120.29, 122.33 (d, J = 169.1 z), 127.39, 127.94, 128.75, 130.28, 131.16, 133.47 (t, J = 41.2 z), 134.42, 136.24, 137.69, 138.63, 147.12, 148.40, 159.92, (d, J = 20.6 z), 160.14, 162.26 (d, J = 24.8 z), 164.67. IR (ATR): 3339 w, 3012 w, 2969 w, 2925 w, 2850 w, 2359 w, 2337 w, 1742 s, 1679 w, 1624 w, 1523 m, 1469 m, 1425 w, 1368 m, 1326 m, 1218 s, 1092 w, 1053 w, 1015 w, 898 w, 771 s. MS, m/z (relative intensity, %): 418 (M +, 9), 401 (12), 284 (67), 275 (29), 260 (18), 171 (12), 141 (100), 113 (17). RMS Calcd for C 24 16 F 2 2 3 418.1129, found 418.1126. 2-phenethyl--(quinolin-8-yl)-1-naphthamide (3aj) 36.6 mg, 67% yield. White solid. Mp = 105.5-106.1 C. R f 0.57 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 1.09 (s, 9), 2.48 (s, 3), 7.02 (d, J = 7.8 z, 1), 7.18 (d, J = 7.8 z, 1), 7.37 (t, J = 8.0 z, 1), 7.46 (dd, J = 8.2, 4.6 z, 1), 7.55-7.62 (c, 2), 8.18 (dd, J = 8.2, 1.8 z, 1), 8.79 (dd, J = 4.1, 1.4 z, 1), 8.95 (dd, J = 6.9, 1.8 z, 1), 10.00 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.43, 26.96, 39.11, 116.81, 120.28, 121.84, 122.16, 127.48, 127.98, 128.03, 130.05, 131.09, 134.44, 136.36, 137.36, 138.45, 147.77, 148.50, 165.09, 177.14. IR (ATR): 2955 m, 2925 m, 2902 w, 1720 m, 1681 s, 1597 s, 1525 s, 1483 w, 1384 w, 1325 m, 1219 w, 1168 m, 1114 s, 826 w, 771 s. MS, m/z (relative intensity, %): 402 (M +, 32), 260 (19), 259 (100), 258 (92), 244 (10), 215 (19), 181 (24), 153 (20), 145 (10), 144 (83), 141 (11), 140 (16), 139 (11), 91 (27). RMS Calcd for C 22 22 2 3 362.1630, found 362.1627. 3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl cyclohexanecarboxylate (3ak) 29.2 mg, 50% yield. White solid. Mp = 112.4-113.0 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : 1.10-0.91 (m, 3), 1.34-1.25 (m, 2), 1.52-1.42 (m, 3), 1.76 (dd, J = 13.3, S8
3.2 z, 2), 2.37 (tt, J = 11.0, 3.7 z, 1), 2.48 (s, 3), 7.03 (d, J = 7.8 z, 1), 7.17 (d, J = 7.8 z, 1), 7.36 (t, J = 8.0 z, 1), 7.46 (q, J = 4.1 z, 1), 7.62-7.55 (m, 2), 8.18 (dd, J = 8.2, 1.4 z, 1), 8.78 (q, J = 2.0 z, 1), 8.93 (dd, J = 6.9, 1.8 z, 1), 10.01 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.54, 25.16, 25.59, 28.68, 43.06, 116.91, 120.40, 121.81, 122.16, 127.47, 128.05, 130.09, 131.03, 134.47, 136.38 (two overlapping peaks), 137.46, 138.53, 147.66, 148.49, 165.11, 174.57. IR (ATR): 3015 w, 2970 w, 2941 w, 1739 s, 1523 w, 1482 w, 1425 m, 1367 m, 1216 m, 1116 w, 772 m. MS, m/z (relative intensity, %): 402 (M +, 32), 260 (19), 259 (100), 258 (92), 244 (10), 215 (19), 181 (24), 153 (20), 145 (10), 144 (83), 141 (11), 140 (16), 139 (11), 91 (27). RMS Calcd for C 24 24 2 3 388.1787, found 388.1787. 3-methyl-2,6-diphenethyl--(quinolin-8-yl)benzamide (3al) The compound 3al was prepared according to general procedure (the amount of Co(acac) 2 was increased to 20 mol%). 20.8 mg, 43% yield. White solid. R f 0.43 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : 2.10 (s, 3), 2.50 (s, 3), 7.05 (d, J = 8.2 z, 1), 7.19 (d, J = 7.8 z, 1), 7.37 (t, J = 7.8 z, 1), 7.45 (q, J = 4.3 z, 1), 7.62-7.56 (m, 2), 8.18 (dd, J = 8.2, 1.4 z, 1), 8.78 (q, J = 1.8 z, 1), 8.94 (dd, J = 6.9, 1.8 z, 1), 10.02 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.70, 20.95, 116.99, 120.44, 121.88, 122.24, 127.50, 128.10, 128.37, 130.22, 130.81, 134.42, 136.44, 137.70, 138.60, 147.59, 148.55, 164.98, 169.70. RMS Calcd for C 19 16 2 3 320.1161, found 320.1160. This compound has been reported previously. 3 4-methoxy-3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ba) The compound 3ba was prepared according to general procedure (the amount of Co(acac) 2 was increased to 40 mol%). 48.5 mg, 76% yield. White solid. Mp = 119.8-120.0 C. R f 0.43 (hexane/etac 3 Zhang, M. J. Chem. Res. 2013, 37, 606. S9
= 31). 1 MR (CDCl 3, 400 Mz) : δ 2.22 (s, 6), 3.89 (s, 3), 6.88 (d, J = 7.8 z, 2), 7.11-7.16 (c, 2), 7.22-7.26 (c, 1), 7.33 (d, J = 8.7 z, 1), 7.48-7.56 (c, 2), 7.71 (d, J = 3.2 z, 1), 7.98 (dd, J = 4.4, 1.6 z, 1), 8.06 (dd, J = 8.2, 1.8 z, 1), 8.93 (dd, J = 7.3, 1.4 z, 1), 11.11 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 20.11, 55.99, 114.77, 116.95, 118.97, 121.44, 122.01, 124.44, 127.35, 127.75, 127.78, 129.16, 130.00, 132.51, 134.80, 136.01, 136.23, 138.57, 141.66, 147.91, 157.74, 163.05, 168.31. IR (ATR): 3344 w, 3056 w, 3026 w, 2959 w, 2863 w, 1675 m, 1596 w, 1579 w, 1521 s, 1482 m, 1424 w, 1386 w, 1326 m, 1261 w, 1169 w, 1126 m, 1080 w, 899 w, 825 w, 791 w, 756 w, 699 w. MS, m/z (relative intensity, %): 420 (M +, 12), 276 (13), 171 (12), 145 (13), 144 (100), 91 (13). RMS Calcd for C 27 24 2 4 440.1736, found 440.1733. 2-(quinolin-8-ylcarbamoyl)-[1,1'-biphenyl]-3-yl 2,6-dimethylbenzoate (3ca) The compound 3ca was prepared according to general procedure (the amount of Co(acac) 2 was increased to 20 mol%). 39.9 mg, 56% yield. White solid. Mp = 190.0-190.5 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.33 (s, 6), 6.94 (d, J = 7.8 z, 2), 7.13 (tt, J = 7.6, 1.7 z, 2), 7.22-7.26 (c, 3), 7.32 (dd, J = 8.2, 4.1 z, 1), 7.37 (dd, J = 8.2, 0.9 z, 1), 7.42-7.49 (c, 3), 7.55-7.63 (c, 3), 8.05 (dd, J = 8.2, 1.4 z, 1), 8.58 (dd, J = 4.1, 1.8 z, 1), 8.71 (dd, J = 6.9, 1.8 z, 1), 9.85 (s, 1). 13 C MR (CDCl 3, 100 Mz) : δ 19.91, 116.67, 121.58, 121.93, 121.96, 127.23, 127.73, 127.86, 128.20, 128.44, 128.79, 129.90, 130.48, 130.88, 132.55, 134.34, 135.78, 136.08, 138.31 (two overlapping peaks), 139.21, 141.79, 148.06, 148.14, 164.45, 168.63. IR (ATR): 3017 w, 2970 w, 2948 w, 2924 w, 1739 s, 1680 w, 1523 w, 1424 w, 1367 m, 1217 s, 1102 w, 1046 w, 771 s. MS, m/z (relative intensity, %): 380 (M +, 3), 237 (18), 236 (18), 145 (32), 144 (100), 117 (12), 105 (15). RMS Calcd for C 31 24 2 3 472.1787, found 472.1782. 2-(quinolin-8-ylcarbamoyl)-3-(trifluoromethyl)phenyl 2,6-dimethylbenzoate (3da) S10
62.9 mg, 90% yield. White solid. Mp = 178.0-178.3 C. R f 0.29 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.26 (s, 6), 6.91 (d, J = 7.3 z, 2), 7.12 (t, J = 7.6 z, 1), 7.41 (dd, J = 8.5, 4.4 z, 1), 7.54-7.59 (c, 3), 7.66-7.73 (c, 2), 8.14 (dd, J = 8.2, 1.8 z, 1), 8.72 (dd, J = 4.4, 1.6 z, 1), 8.87 (dd, J = 5.0, 3.7 z, 1), 10.19 (s, 1). 13 C MR (CDCl 3, 101 Mz) :δ 19.88, 117.05, 121.85, 122.56, 124.16, 124.27 (q, J = 16.4 z), 127.23 (d, J = 82.4 z), 127.80, 127.93, 128.82, 129.14, 129.46, 129.81, 130.17, 130.76, 131.81, 134.13, 136.05 (d, J = 210.4 z), 138.33, 148.39, 148.55, 161.88, 168.17. IR (ATR): 3333 w, 3007 w, 2955 w, 2925 w, 2852 w, 1750 m, 1712 s, 1686 m, 1581 w, 1524 s, 1486 m, 1463 m, 1424 m, 1360 m, 1318 s, 1262 w, 1220 s, 1173 m, 1132 m, 1099 w, 1081 w, 1028 m. MS, m/z (relative intensity, %): 422 (M +, 2), 263 (11), 223 (16), 145 (18), 144 (100), 57 (10). RMS Calcd for C 26 19 2 3 464.1348, found 464.1352. 4-methoxy-3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ea) 61.2 mg, 92% yield. White solid. Mp = 189.8-190.1 C. R f 0.43 (hexane/etac = 31). 1 MR (CDCl 3, 400 Mz) : δ 2.23 (s, 6), 2.34 (s, 3), 3.91 (s, 3), 6.91 (d, J = 7.3 z, 2), 6.99 (d, J = 9.2 z, 1), 7.08-7.16 (c, 2), 7.42 (dd, J = 8.2, 4.1 z, 1), 7.54-7.60 (c, 2), 8.15 (dd, J = 8.2, 1.8 z, 1), 8.73 (dd, J = 4.4, 1.6 z, 1), 8.93 (dd, J = 6.9, 1.8 z, 1), 10.15 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 13.22, 19.79, 56.12, 111.55, 116.96, 120.59, 121.80, 122.23, 125.66, 127.37, 127.64, 128.00, 129.73, 132.78, 134.41, 135.56 (two overlapping peaks), 136.30, 138.48, 140.38, 148.48, 155.95, 164.93, 169.11. IR (ATR): 3338 w, 3012 w, 2928 w, 2834 w, 1745 m, 1679 m, 1595 w, 1523 w, 1479 s, 1425 m, 1385 m, 1326 m, 1302 w, 1272 m, 1220 s, 1146 w, 1098 s, 1052 s, 827 s. MS, m/z (relative intensity, %): 420 (M +, 12), 276 (13), 171 (12), 145 (13), 144 (100), 91 (13). RMS Calcd for C 27 24 2 4 440.1736, found 440.1733. 4-acetoxy-3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3fa) S11
63.4 mg, 90% yield. White solid. Mp = 115.5-116.0 C. R f 0.34 (exane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.25 (s, 6), 2.31 (s, 3), 2.38 (s, 3), 6.90 (d, J = 7.8 z, 2), 7.10 (t, J = 7.8 z, 1), 7.24 (s, 2), 7.42 (dd, J = 8.2, 4.1 z, 1), 7.55-7.58 (c, 2), 8.15 (dd, J = 8.2, 1.8 z, 1), 8.74 (dd, J = 4.1, 1.4 z, 1), 8.90 (dd, J = 6.0, 2.7 z, 1), 10.17 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 13.59, 19.86, 20.96, 117.04, 121.29, 121.88, 122.42, 124.11, 127.33, 127.70, 127.98, 129.72, 129.91, 132.40, 132.95, 134.27, 135.69, 136.31, 138.45, 144.98, 147.35, 148.56, 164.06, 168.39, 169.21. IR (ATR): 3015 w, 2970 w, 2943 w, 1738 s, 1437 w, 1368 m, 1214 m, 772 m. MS, m/z (relative intensity, %): 342 (M +, 100), 313 (16), 297 (13), 251 (35), 223 (14), 197 (12), 171 (25), 144 (51), 141 (11), 91 (14). RMS Calcd for C 28 24 2 5 468.1685, found 468.1686. 3,4-dimethyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ga) 60.4 mg, 94% yield. White solid. Mp = 185.1-185.5 C. R f 0.43 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.23 (s, 6), 2.34 (s, 3), 2.36 (s, 3), 6.89 (d, J = 7.8 z, 2), 7.07-7.11 (c, 2), 7.31 (d, J = 8.2 z, 1), 7.41 (dd, J = 8.2, 4.1 z, 1), 7.53-7.59 (c, 2), 8.14 (dd, J = 8.2, 1.8 z, 1), 8.72 (dd, J = 4.4, 1.6 z, 1), 8.93 (dd, J = 7.1, 2.1 z, 1), 10.13 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 16.86, 19.78, 20.00, 116.97, 119.90, 121.80, 122.22, 127.39, 127.64, 128.00, 129.75, 131.50, 131.83, 132.75, 134.45, 135.35, 135.58, 135.65, 136.31, 138.49, 145.40, 148.48, 165.71, 168.87. IR (ATR): 3335 w, 3014 w, 2970 w, 2925 w, 1739 s, 1679 w, 1523 m, 1483 w, 1424 w, 1368 m, 1219 s, 1102 w, 1053 w, 771 s. MS, m/z (relative intensity, %): 356 (19), 355 (M +, 74), 264 (44), 213 (11), 212 (75), 211 (50), 210 (11), 197 (14), 185 (16), 184 (48), 183 (18), 182 (20), 172 (12), 171 (100), 170 (13), 144 (40), 94 (89), 93 (18). RMS Calcd for C 27 24 2 3 424.1787, found 424.1783. 5-(quinolin-8-ylcarbamoyl)-2,3-dihydrobenzo[b][1,4]dioxin-6-yl 2,6-dimethylbenzoate (3ha) The compound 3ha was prepared according to general procedure (the amount of Co(acac) 2 and S12
Ag 2 C 3 were increased to 20 mol% and 0.30 mmol, respectively).30.8 mg, 45% yield. White solid. Mp = 188.8-189.0 C. R f 0.14 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.29 (s, 6), 4.30-4.34 (c, 4), 6.82 (d, J = 9.2 z, 1), 6.92 (d, J = 7.8 z, 2), 7.03 (d, J = 8.7 z, 1), 7.11 (t, J = 7.6 z, 1), 7.41 (dd, J = 8.2, 4.1 z, 1), 7.51-7.57 (c, 2), 8.13 (dd, J = 8.5, 1.6 z, 1), 8.74 (dd, J = 4.4, 1.6 z, 1), 8.92 (dd, J = 6.9, 1.8 z, 1), 10.34 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.90, 64.10, 64.75, 115.50, 116.99, 118.72, 121.11, 121.72, 122.08, 127.45, 127.70, 128.00, 129.83, 132.57, 134.62, 135.76, 136.29, 138.52, 141.52, 141.59, 142.00, 148.39, 161.83, 168.81. IR (ATR): 3016 w, 2955 w, 2925 w, 2852 w, 1742 s, 1679 w, 1525 m, 1481 m, 1377 m, 1328 w, 1299 w, 1263 m, 1219 s, 1078 m, 1048 w, 766 s. MS, m/z (relative intensity, %): 454 (M +, 19), 134 (10), 133 (100), 105 (15). RMS Calcd for C 27 22 2 5 454.1529, found 454.1528. 4-methoxy-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ia) 34.7 mg, 55% yield. White solid. Mp = 135.0-135.1 C. R f 0.43 (hexane/etac = 31). 1 MR (CDCl 3, 400 Mz) : δ 2.32 (s, 6), 3.90 (s, 3), 6.95 (t, J = 7.6 z, 4), 7.13 (t, J = 7.6 z, 1), 7.41 (dd, J = 8.2, 4.1 z, 1), 7.46-7.58 (c, 3), 8.14 (dd, J = 8.2, 1.4 z, 1), 8.75 (dd, J = 4.1, 1.8 z, 1), 8.93 (dd, J = 7.3, 1.4 z, 1), 10.32 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 20.11, 55.99, 114.77, 116.95, 118.97, 121.44, 122.01, 124.44, 127.35, 127.75, 127.78, 129.16, 130.00, 132.51, 134.80, 136.01, 136.23, 138.57, 141.66, 147.91, 157.74, 163.05, 168.31. IR (ATR): 3005 w, 2957 w, 2922 w, 2852 w, 1745 m, 1679 m, 1605 w, 1525 s, 1468 m, 1423 m, 1383 w, 1327 w, 1261 w, 1219 s, 1080 s, 770 s. MS, m/z (relative intensity, %): 426 (M +, 11), 134 (10), 133 (100), 105 (16). RMS Calcd for C 27 24 2 4 426.1580, found 426.1576. 6-fluoro-3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ja) 55.2 mg, 87% yield. White solid. Mp = 184.0-184.2 C. R f 0.43 (hexane/etac = 31). 1 MR S13
(CDCl 3, 400 Mz) : δ 2.28 (s, 6), 2.46 (s, 3), 6.92 (d, J = 7.8 z, 2), 7.12 (t, J = 7.6 z, 1), 7.18-7.16 (c, 3), 7.43 (dd, J = 8.2, 4.1 z, 1), 7.56-7.61 (c, 2), 8.16 (dd, J = 8.2, 1.4 z, 1), 8.73 (dd, J = 4.1, 1.8 z, 1), 8.91 (dd, J = 6.0, 3.2 z, 1), 10.15 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 18.98, 19.88, 117.05, 117.22, 117.41, 122.2 (d, J = 236.0 z), 127.34, 127.74, 127.99, 129.14 (d, J = 28.8 z), 130.05, 131.85, 132.12 (d, J = 12.4 z), 133.26, 134.16, 134.94, 135.09, 136.26, 136.37, 138.41, 148.60, 151.36, 153.84, 163.91 (d, J = 8.4 z), 167.12. IR (ATR): 3337 w, 3014 w, 2970 w, 2925 w, 1740 s, 1680 w, 1523 m, 1484 m, 1424 w, 1367 m, 1326 w, 1255 w, 1219 s, 1100 w, 1049 w, 1008 w, 777 s. MS, m/z (relative intensity, %): 393 (30), 392 (M +, 100), 301 (37), 249 (14), 248 (27), 247 (17), 219 (33), 171 (56), 145 (15), 144 (88), 131 (16), 102 (10), 91 (17). RMS Calcd for C 26 21 F 2 3 428.1536, found 428.1532. 6-bromo-3-methyl-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ka) 46.9 mg, 64% yield. White solid. Mp = 198.0-198.5 C. R f 0.29 (hexane/etac = 31). 1 MR (CDCl 3, 400 Mz) : δ 2.42 (s, 6), 2.44 (s, 3), 6.91 (d, J = 7.8 z, 2), 7.08-7.13 (c, 2), 7.40 (dd, J = 8.2, 4.1 z, 1), 7.54-7.56 (c, 2), 7.64 (d, J = 8.2 z, 1), 8.12 (dd, J = 8.2, 1.8 z, 1), 8.73 (dd, J = 4.1, 1.8 z, 1), 8.87 (dd, J = 6.2, 2.5 z, 1), 10.17 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 19.23, 21.17, 114.35, 117.02, 121.88, 122.52, 127.26, 128.01, 128.38, 129.75, 130.51, 130.64, 133.80, 134.04, 134.13, 136.30, 136.69, 137.88, 138.47, 145.20, 148.61, 164.33, 166.93. IR (ATR): 3017 w, 2970 w, 2943 w 1739 s, 1678 w, 1524 w, 1481 w, 1425 w, 1367 m, 1217 s, 1094 w, 1050 w, 771 s. MS, m/z (relative intensity, %): 396 (M +, 2), 252 (11), 145 (23), 144 (100), 121 (34). RMS Calcd for C 26 21 Br 2 3 488.0736, found 488.0730. 3,6-difluoro-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3la) 33.4 mg, 52% yield. White solid. Mp = 135.0-135.1 C. R f 0.29 (hexane/etac = 3/1). 1 MR S14
(CDCl 3, 400 Mz) : δ 2.36 (s, 6), 6.97 (d, J = 7.3 z, 2), 7.13-7.18 (c, 2), 7.34 (td, J = 9.2, 4.6 z, 1), 7.43 (dd, J = 8.3, 4.1 z, 1), 7.57 (d, J = 4.6 z, 2), 8.16 (dd, J = 8.5, 1.6 z, 1), 8.74 (dd, J = 4.4, 1.6 z, 1), 8.87 (t, J = 4.4 z, 1), 10.33 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 20.06, 114.54 (dd, J = 28.8 z, 99.2 z), 117.14, 118.36 (dd, J = 86.8 z, 37.2 z), 121.93 (d, J = 37.2 z), 122.69, 127.35, 127.50, 127.94 (d, J = 24.8 z), 130.34, 131.35, 134.07, 136.40, 136.47, 136.57, 138.38, 148.60, 150.01 (d, J = 12.0 z), 152.49, 154.00, 156.49 (d, J = 8.4 z), 158.75, 166.61. IR (ATR): 3015 w, 2970 w, 2944 w, 1739 s, 1546 w, 1437 w, 1437 m, 1367 m, 1217 w, 1088 w, 772 s. MS, m/z (relative intensity, %): 442 (M +, 2), 167 (23), 145 (23), 144 (100). RMS Calcd for C 25 18 2 3 432.1285, found 432.1287. 3-fluoro-5-methoxy-2-(quinolin-8-ylcarbamoyl)phenyl 2,6-dimethylbenzoate (3ma) The compound 3ma was prepared according to general procedure (the amount of Co(acac) 2 was increased to 20 mol%). 47.7 mg, 72% yield. White solid. Mp = 116.8-117.0 C. R f 0.23 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.36 (s, 6), 3.88 (s, 3), 6.68-6.72 (c, 2), 6.95 (d, J = 7.8 z, 2), 7.14 (t, J = 7.6 z, 1), 7.40 (dd, J = 8.2, 4.1 z, 1), 7.51-7.57 (c, 2), 8.13 (dd, J = 8.2, 1.4 z, 1), 8.70 (dd, J = 4.1, 1.8 z, 1), 8.88 (dd, J = 6.6, 2.1 z, 1), 10.36 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 20.16, 56.12, 99.84, 100.11, 105.93, 113.08, 116.87, 121.74, 122.13, 127.65 (d, J = 205.2 z), 127.96, 130.15, 131.90, 134.57, 136.24 (d, J = 30.4 z), 138.49, 148.38, 150.15, 150.23, 159.91 (d, J = 16.0 z), 161.98, 162.11, 162.37, 167.77. IR (ATR): 3017 w, 2970 w, 2945 w, 2925 w, 1739 s, 1628 w, 1527 w, 1425 w, 1367 m, 1218 s, 1150 w, 1102 w, 1056 w, 771 s. MS, m/z (relative intensity, %): 384 (M +, 15), 241 (41), 240 (42), 145 (34), 144 (100), 117 (17), 109 (16). RMS Calcd for C 25 21 F 2 444.1485, found 384.1636. 1-(quinolin-8-ylcarbamoyl)naphthalen-2-yl 2,6-dimethylbenzoate (3na) S15
56.7 mg, 86% yield. White solid. Mp = 162.6-163.1 C. R f 0.43 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) : δ 2.30 (s, 6), 6.92 (d, J = 7.3 z, 2), 7.11 (t, J = 7.6 z, 1), 7.38 (dd, J = 8.2, 4.1 z, 1), 7.47 (d, J = 8.7 z, 1), 7.52-7.64 (m, 4), 7.94 (dd, J = 6.2, 3.4 z, 1), 8.03 (d, J = 8.7 z, 1), 8.09 (dd, J = 6.2, 3.4 z, 1), 8.14 (dd, J = 8.5, 1.6 z, 1), 8.63 (dd, J = 4.1, 1.4 z, 1), 9.05 (dd, J = 7.3, 1.4 z, 1), 10.36 (s, 1). 13 C MR (CDCl 3, 101 Mz): δ 19.90, 76.84, 77.16, 77.36, 77.47, 117.12, 121.54, 121.82, 122.41, 125.28, 126.54, 127.41, 127.74, 127.91, 128.01, 128.35, 129.95, 131.14, 131.23, 131.83, 132.46, 134.51, 135.72, 136.30, 138.46, 144.99, 148.49, 164.55, 168.63. IR (ATR): 3015 w, 2970 w, 2947 w, 1739 s, 1674 w, 1522 w, 1425 w, 1367 s, 1217 m, 1100 w, 1048 w, 772 s. MS, m/z (relative intensity, %): 444 (M +, 6), 303 (14), 302 (14), 301 (15), 300 (13), 145 (26), 144 (100). RMS Calcd for C 29 22 2 3 446.1630, found 446.1629. 2-(quinolin-8-ylcarbamoyl)thiophen-3-yl 2,6-dimethylbenzoate (3na) The compound 3na was prepared according to general procedure (the amount of Co(acac) 2 was increased to 20 mol%). 46.3 mg, 77% yield. White solid. Mp = 145.8-146.0 C. R f 0.23 (hexane/etac = 3/1). 1 MR (CDCl 3, 400 Mz) :δ 2.40 (s, 6), 7.12 (d, J = 7.8 z, 2), 7.19 (dd, J = 8.2, 4.6 z, 1), 7.35 (t, J = 7.6 z, 1), 7.41 (d, J = 5.5 z, 1), 7.45 (dd, J = 8.2, 1.4 z, 1), 7.54-7.49 (m, 2), 7.58 (d, J = 5.3 z, 1), 8.03 (dd, J = 8.2, 1.8 z, 1), 8.86 (dd, J = 7.3, 1.4 z, 1), 11.20 (s, 1). 13 C MR (CDCl 3, 101 Mz) : δ 20.50, 116.97, 121.42, 121.85, 122.72, 126.29, 127.41, 127.80, 128.22, 129.16, 130.55, 132.10, 134.72, 136.04, 136.94, 138.55, 145.39, 147.86, 158.89, 166.50. IR (ATR): 3016 w, 2970 w, 2943 w, 2924 w, 2852 w, 1739 s, 1654 w, 1531 w, 1431 w, 1367 m, 1217 s, 1096 w, 1043 w, 771 s. MS, m/z (relative intensity, %): 456 (M +, 50), 314 (16), 313 (100), 312 (70), 144 (20), 132 (15). RMS Calcd for C 23 18 2 3 S 402.1038, found 402.1037. VI. Deuterium Labeling Experiments S16
D D CD 3 D D 1a-d 7 0.15 mmol ArC (2a) 0.225 mmol cat. Co(acac) 2 10 mol% Ag 2 C 3 0.20 mmol DCE 0.5 ml 100 C, 30 min under air D D CD 3 D D 1a-d 7 68% 98% (D) + D D CD 3 2 CAr D 3aa-d 6 19% S17
VII. Copies of 1 and 13 C MR Spectra S18
S19
S20
3ab S21
3ab S22
3ac S23
3ac S24
Ph 3ad S25
Ph 3ad S26
F 3ae S27
F 3ae S28
Cl 3af S29
Cl 3af S30
S31
S32
Br 3ah S33
Br 3ah S34
F F 3ai S35
F F 3ai S36
3aj S37
S38
3ak S39
3ak S40
C3 3al S41
C3 3al S42
Me 3ba S43
Me 3ba S44
Ph 3ca S45
Ph 3ca S46
CF 3 3da S47
CF 3 3da S48
Me 3ea S49
Me 3ea S50
Ac 3fa S51
Ac 3fa S52
3ga S53
3ga S54
3ha S55
3ha S56
Me 3ia S57
Me 3ia S58
F 3ja S59
F 3ja S60
Br 3ka S61
Br 3ka S62
F F 3la S63
F F 3la S64
F Me 3ma S65
F Me 3ma S66
3na S67
3na S68
S 3oa S69
S 3oa S70