Iodine-catalyzed synthesis of sulfur-bridged enaminones and chromones via double C(sp 2 )-H thiolation

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Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 2017 Iodine-catalyzed synthesis of sulfur-bridged enaminones and chromones via double C(sp 2 )-H thiolation Yong Gao, a Li Wei, a Yunyun Liu a, * and Jie-Ping Wan a, * Contents General experimental information...s1 Characterization data of all products....s2-s11 References..S12 1H and 13C NMR spectra of all products..s13-s38 General experimental information All experiments were carried out under air atmosphere. The enaminones 1 were synthesized following literature process, 1-2 other chemicals and solvents used in the experiments were obtained from commercial sources and used directly without further treatment. 1 H and 13 C NMR spectra were recorded in 400 MHz apparatus in CDCl 3. The frequencies for 1 H NMR and 13 C NMR test are 400 MHz and 100 MHz, respectively. The chemical shifts were reported in ppm with TMS as internal standard. Melting points were tested in X-4A instrument without correcting temperature and the HRMS data for all new products were obtained under ESI model with TOF analyzer. S1

Characterization data of all products (2E,2'E)-2,2'-Thiobis(1-phenyl-3-(p-tolylamino)prop-2-en-1-one) (4a). Yellow solid; mp 247-250 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.21 (d, J = 13.6 Hz, 2 H), 8.03 (d, J = 13.7 Hz, 2 H), 7.59-7.57 (m, 4 H), 7.52-7.43 (m, 6 H), 7.12-7.06 (m, 8 H), 2.30 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.1, 153.2, 140.0, 137.5, 133.9, 130.6, 130.2, 128.6, 128.4, 116.8, 107.4, 20.8; ESI-HRMS Calcd for C 32 H 29 N 2 O 2 S [M + H] + 505.1944, found 505.1945. O O S HN NH (2E,2'E)-2,2'-Thiobis(1-(p-tolyl)-3-(p-tolylamino)prop-2-en-1-one) (4b). Yellow solid; mp 210-214 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.23 (d, J = 13.6 Hz, 2 H), 8.05 (d, J = 13.6 Hz, 2 H), 7.50 (d, J = 7.8 Hz, 4 H), 7.25-7.23 (m, 4 H), 7.12-7.07 (m, 8 H), 2.42 (s, 6 H), 2.30 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.1, 152.8, 141.0, 137.7, 137.1, 133.7, 130.2, 129.0, 128.9, 116.8, 107.4, 21.5, 20.8; ESI-HRMS Calcd for C 34 H 33 N 2 O 2 S [M + H] + 533.2257, found 533.2256. (2E,2'E)-2,2'-Thiobis(1-(3-methoxyphenyl)-3-(p-tolylamino)prop-2-en-1-one) (4c). Yellow solid; mp 200-201 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.19 (d, J = 13.7 Hz, 2 S2

H), 8.07 (d, J = 13.7 Hz, 2 H), 7.36 (t, J = 7.9 Hz, 2 H), 7.14-7.02 (m, 14 H), 3.83 (s, 6 H), 2.30 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 194.8, 159.6, 153.3, 141.4, 137.5, 134.0, 130.2, 129.3, 121.0, 116.8, 116.6, 113.6, 107.3, 55.4, 20.8; IR (KBr, cm -1 ) 3141, 3026, 2925, 2858, 1629, 1520, 1464, 1349, 1269, 1120, 1042, 813, 792; ESI-HRMS Calcd for C 34 H 33 N 2 O 4 S [M + H] + 565.2156, found 565.2154. (2E,2'E)-2,2'-Thiobis(1-(o-tolyl)-3-(p-tolylamino)prop-2-en-1-one) (4d). Yellow solid; mp 205-208 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.02 (d, J = 13.3 Hz, 2 H), 7.81 (d, J = 13.7 Hz, 2 H), 7.34-7.20 (m, 8 H), 7.08-6.98 (m, 8 H), 2.27 (s, 6 H), 2.18 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 196.2, 153.6, 139.9, 137.2, 135.3, 134.2, 130.7, 130.2, 129.2, 127.0, 125.5, 116.9, 109.3, 20.8, 19.2; ESI-HRMS Calcd for C 34 H 33 N 2 O 2 S [M + H] + 533.2257, found 533.2258. O O S Cl HN NH Cl (2E,2'E)-2,2'-Thiobis(1-(4-chlorophenyl)-3-(p-tolylamino)prop-2-en-1-one) (4e). Yellow solid; mp 254-256 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.19 (d, J = 13.6 Hz, 2 H), 7.98 (d, J = 13.7 Hz, 2 H), 7.54-7.42 (m, 8 H), 7.15-7.05 (m, 8 H), 2.32 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 193.7, 153.0, 138.3, 137.3, 136.9, 134.3, 130.3, 130.0, 128.7, 116.8, 107.2, 20.8; ESI-HRMS Calcd for C 32 H 27 Cl 2 N 2 O 2 S [M + H] + 573.1165, found 573.1165. S3

MeO O S O OMe MeO HN NH OMe (2E,2'E)-2,2'-Thiobis(1-(3,4-dimethoxyphenyl)-3-(p-tolylamino)prop-2-en-1-one) (4f). Yellow solid; mp 230-232 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.23 (d, J = 13.6 Hz, 2 H), 8.09 (d, J = 13.6 Hz, 2 H), 7.23-7.08 (m, 12 H), 6.92 (d, J = 8.2 Hz, 2 H), 3.96 (s, 6 H), 3.91 (s, 6 H), 2.31 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 194.4, 152.2, 151.5, 148.9, 137.8, 133.6, 132.5, 130.2, 122.6, 116.6, 112.0, 110.3, 107.0, 56.0, 20.8; IR (KBr, cm -1 ) 3016, 2931, 2853, 2360, 1643, 1576, 1459, 1336, 1269, 1131, 1019, 864, 797; ESI-HRMS Calcd for C 36 H 37 N 2 O 6 S [M + H] + 625.2367, found 625.2367. O O Cl S Cl Cl HN NH Cl (2E,2'E)-2,2'-Thiobis(1-(3,4-dichlorophenyl)-3-(p-tolylamino)prop-2-en-1-one) (4g). Yellow solid; mp 233-235 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.18 (d, J = 13.2 Hz, 2 H), 7.98-7.94 (m, 2 H), 7.67 (s, 2 H), 7.54-7.52 (m, 2 H), 7.39 (d, J = 8.1 Hz, 2 H), 7.25 (d, J = 2.5 Hz, 1 H), 7.16-7.06 (m, 7 H), 2.32 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 192.1, 153.1, 139.7, 137.1, 135.0, 134.6, 133.1, 130.6, 130.4, 127.7, 116.9, 106.9, 20.8; ESI-HRMS Calcd for C 32 H 25 Cl 4 N 2 O 2 S [M + H] + 641.0385, found 641.0388. (2E,2'E)-2,2'-Thiobis(1-(naphthalen-2-yl)-3-(p-tolylamino)prop-2-en-1-one) (4h). S4

Yellow solid; mp 238-241 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.32 (d, J = 13.7 Hz, 2 H), 8.16-8.08 (m, 4 H), 7.92 (t, J = 6.8 Hz, 6 H), 7.71 (d, J = 9.7 Hz, 2 H), 7.61-7.54 (m, 4 H), 7.09 (s, 8 H), 2.29 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.1, 153.2, 137.5, 137.3, 134.4, 133.9, 132.6, 130.2, 128.8, 128.3, 127.8, 127.4, 126.8, 125.8, 116.8, 107.6, 20.8; ESI-HRMS Calcd for C 40 H 33 N 2 O 2 S [M + H] + 605.2257, found 605.2257. (2E,2'E)-2,2'-Thiobis(1-(thiophen-2-yl)-3-(p-tolylamino)prop-2-en-1-one) (4i). Yellow solid; mp 204-206 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.22 (d, J = 13.6 Hz, 2 H), 8.39 (d, J = 13.6 Hz, 2 H), 7.59-7.53 (m, 4 H), 7.15-7.13 (m, 10 H), 2.31 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 185.8, 151.1, 143.5, 137.7, 133.8, 131.1, 131.0, 130.2, 127.4, 116.9, 106.6, 20.8; ESI-HRMS Calcd for C 28 H 25 N 2 O 2 S 3 [M + H] + 517.1073, found 517.1073. (2E,2'E)-2,2'-Thiobis(5-methyl-1-(p-tolylamino)hex-1-en-3-one) (4j). Yellow solid; mp 124-127 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 12.18 (d, J = 12.8 Hz, 2 H), 7.89 (d, J = 13.0 Hz, 2 H), 7.18-7.03 (m, 8 H), 2.75 (d, J = 6.9 Hz, 4 H), 2.33 (s, 6 H), 2.26-2.19 (m, 2 H), 0.98 (d, J = 6.6 Hz, 12 H); 13 C NMR (100 MHz, CDCl 3 ): 202.5, 152.7, 136.6, 135.0, 130.4, 117.3, 102.1, 49.1, 25.4, 22.8, 20.8; IR (KBr, cm -1 ) 3037, 2963, 2925, 2864, 1869, 1613, 1571, 1469, 1349, 1291, 1160, 1056, 808; ESI-HRMS Calcd for C 28 H 37 N 2 O 2 S [M + H] + 465.2570, found 465.2570. S5

(2E,2'E)-2,2'-Thiobis(1-phenyl-3-(phenylamino)prop-2-en-1-one) (4k). Yellow solid; mp 223-225 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.26 (d, J = 13.2 Hz, 2 H), 8.07 (d, J = 13.6 Hz, 2 H), 7.60-7.30 (m, 14 H), 7.19-7.06 (m, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.3, 153.1, 139.9, 139.9, 130.8, 129.7, 128.7, 128.4, 124.2, 116.8, 107.9; IR (KBr, cm -1 ) 3021, 1629, 1581, 1482, 1349, 1272, 1117, 1024, 874, 789; ESI-HRMS Calcd for C 30 H 25 N 2 O 2 S [M + H] + 477.1631, found 477.1632. (2E,2'E)-2,2'-Thiobis(1-phenyl-3-(o-tolylamino)prop-2-en-1-one) (4l). Yellow solid; mp 188-191 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 10.57 (d, J = 13.3 Hz, 2 H), 7.99 (d, J = 13.4 Hz, 2 H), 7.52-7.38 (m, 10 H), 7.22 (d, J = 7.3 Hz, 2 H), 7.13-7.02 (m, 4 H), 6.85 (d, J = 7.8 Hz, 2 H), 2.65 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 194.9, 155.8, 140.3, 139.0, 131.5, 130.4, 129.5, 128.5, 128.3, 126.9, 124.8, 118.0, 107.7, 18.2; ESI-HRMS Calcd for C 32 H 29 N 2 O 2 S [M + H] + 505.1944, found 505.1945. O S O HN NH MeO OMe (2E,2'E)-2,2'-Thiobis(3-((3-methoxyphenyl)amino)-1-phenylprop-2-en-1-one) (4m). Brown solid; mp 180-184 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.19 (d, J = 13.5 Hz, 2 H), 8.03 (d, J = 13.5 Hz, 2 H), 7.60-7.44 (m, 10 H), 7.22 (t, J = 8.1 Hz, 2 H), S6

6.78-6.73 (m, 4 H), 6.63 (d, J = 8.2 Hz, 2 H), 3.80 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.3, 160.8, 153.0, 141.2, 139.8, 130.9, 130.5, 128.7, 128.4, 109.4, 109.3, 108.0, 103.1, 55.4; ESI-HRMS Calcd for C 32 H 29 N 2 O 4 S [M + H] + 537.1843, found 537.1843. (2E,2'E)-2,2'-Thiobis(3-((3-chlorophenyl)amino)-1-phenylprop-2-en-1-one) (4n). Yellow solid; mp 220-225 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.30 (d, J = 13.3 Hz, 2 H), 8.00 (d, J = 13.3 Hz, 2 H), 7.61-7.47 (m, 10 H), 7.25-7.22 (m, 2 H), 4.14-7.04 (m, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.5, 152.6, 141.2, 139.4, 135.5, 131.2, 130.8, 128.8, 128.5, 124.1, 116.8, 115.2, 108.8; ESI-HRMS Calcd for C 30 H 23 Cl 2 N 2 O 2 S [M + H] + 545.0852, found 545.0851. (2E,2'E)-2,2'-Thiobis(3-((3-nitrophenyl)amino)-1-phenylprop-2-en-1-one) (4o). Yellow solid; mp 144-145 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 12.25 (d, J = 11.3 Hz, 2 H), 7.97-7.89 (m, 6 H), 7.56-7.46 (m, 10 H), 7.37 (d, J = 8.0 Hz, 2 H), 6.16 (d, J = 8.0 Hz, 2 H); 13 C NMR (100 MHz, CDCl 3 ): 191.8, 149.4, 143.4, 141.7, 138.6, 132.1, 130.6, 128.6, 127.5, 122.2, 117.8, 110.0, 95.7; ESI-HRMS Calcd for C 30 H 23 N 4 O 6 S [M + H] + 567.1333, found 567.1328. S7

(2E,2'E)-2,2'-Thiobis(3-((4-bromophenyl)amino)-1-phenylprop-2-en-1-one) (4p). Yellow solid; mp 247-248 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.28 (d, J = 13.5 Hz, 2 H), 7.99 (d, J = 13.4 Hz, 2 H), 7.59-7.41 (m, 14 H), 7.05 (d, J = 8.5 Hz, 4 H); 13 C NMR (100 MHz, CDCl 3 ): 195.5, 152.7, 139.5, 139.0, 132.7, 131.1, 128.7, 128.5, 118.3, 116.8, 108.5; ESI-HRMS Calcd for C 30 H 23 Br 2 N 2 O 2 S [M + H] + 632.9842, found 632.9841. (2E,2'E)-2,2'-Thiobis(3-((4-fluorophenyl)amino)-1-phenylprop-2-en-1-one) (4q). Yellow solid; mp 229-233 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.32 (d, J = 13.5 Hz, 2 H), 7.98 (d, J = 13.5 Hz, 2 H), 7.59-7.45 (m, 10 H), 7.16-7.12 (m, 4 H), 7.02 (t, J = 8.6 Hz, 4 H); 13 C NMR (100 MHz, CDCl 3 ): 195.3, 160.8, 158.4, 153.4, 139.7, 136.2, 130.9, 128.6, 128.5, 118.3, 118.2, 116.6, 116.4, 107.9; IR (KBr, cm -1 ) 3067, 2976, 2861, 1642, 1600, 1469, 1352, 1272, 1117, 1029, 880, 720; ESI-HRMS Calcd for C 32 H 23 F 2 N 2 O 2 S [M + H] + 513.1443, found 513.1442. S8

(2E,2'E)-2,2'-Thiobis(3-((4-iodophenyl)amino)-1-phenylprop-2-en-1-one) (4r). Yellow solid; mp 241-242 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.26 (d, J = 13.3 Hz, 2 H), 7.99 (d, J = 13.4 Hz, 2 H), 7.62-7.45 (m, 14 H), 6.94 (d, J = 8.6 Hz, 4 H ); 13 C NMR (100 MHz, CDCl 3 ): 195.5, 152.5, 139.7, 139.5, 138.6, 131.1, 128.7, 128.5, 118.7, 108.6, 87.1; ESI-HRMS Calcd for C 30 H 23 I 2 N 2 O 2 S [M + H] + 728.9564, found 728.9564. Diethyl 4,4'-(((1E,1'E)-thiobis(3-oxo-3-phenylprop-1-ene-2,1-diyl))bis(azanediyl)) dibenzoate (4s). Yellow solid; mp 219-222 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.39 (d, J = 13.3 Hz, 2 H), 8.10 (d, J = 13.3 Hz, 2 H), 8.01 (d, J = 8.7 Hz, 4 H), 7.62-7.47 (m, 10 H), 7.20 (d, J = 8.8 Hz, 4 H), 4.35 (q, J = 7.1 Hz, 4 H), 1.38 (t, J = 7.1 Hz, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 195.7, 165.9, 152.1, 143.6, 139.3, 131.5, 131.3, 128.8, 128.6, 125.9, 116.0, 109.5, 60.9, 14.3; ESI-HRMS Calcd for C 36 H 33 N 2 O 6 S [M + H] + 621.2054, found 621.2054. (2E,2'E)-2,2'-Thiobis(3-((2,4-dimethylphenyl)amino)-1-phenylprop-2-en-1-one) (4t). Yellow solid; mp 198-202 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 10.56 (d, J = 13.3 Hz, 2 H), 7.93 (d, J = 13.4 Hz, 2 H), 7.51-7.36 (m, 10 H), 7.02 (s, 2 H), 6.91 (d, J = 7.8 Hz, 2 H), 6.75 (d, J = 8.0 Hz, 2 H), 2.59 (s, 6 H), 2.27 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 194.8, 156.2, 140.4, 136.8, 134.7, 132.1, 130.3, 129.6, 128.5, 128.3, 127.4, 118.5, 107.2, 20.7, 18.1; IR (KBr, cm -1 ) 3123, 3037, 2957, 2856, 2360, 1619, S9

1592, 1461, 1384, 1269, 1112, 1024, 861, 723; ESI-HRMS Calcd for C 34 H 33 N 2 O 2 S [M + H] + 533.2257, found 533.2257. (2E,2'E)-2,2'-Thiobis(3-((4-methylpyridin-2-yl)amino)-1-phenylprop-2-en-1-one) (4u). Yellow solid; mp 250-254 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.40 (d, J = 12.6 Hz, 2 H), 8.83 (d, J = 12.7 Hz, 2 H), 8.02 (d, J = 5.1 Hz, 2 H), 7.62 (d, J = 6.9 Hz, 4 H), 7.54-7.44 (m, 6 H), 7.15 (s, 2 H), 6.77 (d, J = 4.9 Hz, 2 H), 2.37 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 196.3, 152.0, 151.5, 150.0, 147.9, 139.7, 130.9, 128.9, 128.4, 120.4, 113.3, 108.9, 21.1; IR (KBr, cm -1 ) 3275, 3058, 2984, 2850, 1907, 1632, 1552, 1472, 1381, 1261, 1112, 1029, 819, 728; ESI-HRMS Calcd for C 30 H 27 N 4 O 2 S [M + H] + 507.1849, found 507.1849. 2,2'-Thiobis(5,5-dimethyl-3-(phenylamino)cyclohex-2-en-1-one) (6a). 3 Yellow solid; mp 198-204 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 10.65 (s, 2 H), 7.41 (t, J = 7.7 Hz, 4 H), 7.29 (s, 1 H), 7.24-7.22 (m, 5 H), 2.44 (s, 4 H), 2.37 (s, 4 H), 1.05 (s, 12 H); 13 C NMR (100 MHz, CDCl 3 ): 195.6, 167.7, 138.0, 129.4, 126.3, 124.7, 103.5, 49.5, 40.8, 32.6. 2,2'-Thiobis(3-((4-chlorophenyl)amino)-5,5-dimethylcyclohex-2-en-1-one) (6b). 3 S10

Yellow solid; mp 278-280 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 11.18 (s, 2 H), 7.35 (d, J = 8.6 Hz, 4 H), 7.20 (d, J = 8.6 Hz, 4 H), 2.58 (s, 4 H), 2.38 (s, 4 H), 0.98 (s, 12 H); 13 C NMR (100 MHz, CDCl 3 ): 194.8, 167.0, 137.3, 131.2, 129.4, 125.7, 104.8, 50.5, 41.3, 32.7; IR (KBr, cm -1 ) 3064, 2957, 2938, 1600, 1590, 1492, 1382, 1277, 1120, 819, 736. 3,3'-Thiobis(4H-chromen-4-one) (8a) 4 White solid; mp 198-199 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 8.62 (s, 2 H), 8.17 (d, J = 8.0 Hz, 2 H), 7.66 (t, J = 8.0 Hz, 2 H), 7.46-7.38 (m, 4 H); 13 C NMR (100 MHz, CDCl 3 ): 175.6, 159.6, 156.3, 133.9, 126.1, 125.7, 123.9, 118.3, 116.5; IR (KBr, cm -1 ) 3059, 1824, 1629, 1469, 1349, 1309, 1219, 1171, 1016, 888, 760. 3,3'-Thiobis(6-methyl-4H-chromen-4-one) (8b). 4 White solid; mp 224-225 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 8.59 (s, 2 H), 7.95 (s, 2 H), 7.45 (d, J = 8.4 Hz, 2 H), 7.33 (d, J = 8.4 Hz, 2 H), 2.42 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 175.7, 159.5, 154.6, 135.8, 135.1, 125.3, 123.6, 118.0, 116.3, 20.9. 3,3'-Thiobis(7-methoxy-4H-chromen-4-one) (8c). White solid; mp 237-239 o C; 1 H NMR (400 MHz, CDCl 3 ): δ 8.53 (s, 2 H), 8.07 (d, J = 8.9 Hz, 2 H), 6.95 (d, J = 7.5 Hz, 2 H), 6.81 (s, 2 H), 3.88 (s, 6 H); 13 C NMR (100 MHz, CDCl 3 ): 175.0, 164.2, 159.2, 158.1, 127.4, 117.8, 116.5, 115.1, 100.4, 55.9; IR (KBr, cm -1 ) 3074, 1850, 1618, 1440, 1360, 1307, 1227, 1187, 1019, 941, 776; ESI-HRMS Calcd for C 20 H 15 O 6 S [M + H] + 383.0584, found 383.0582. S11

References (1) F. M. A. A. EL-Taweel and M. H. Elnagdi, J. Heterocyclic Chem., 2001, 38, 981. (2) G. W. Wang and C. B. Miao, Green Chem., 2006, 8, 1080. (3) L. F. Yang, C. G. Liu, X. P. Xu and S. J. Ji, Org. Biomol. Chem., 2016, 14, 2993. (4) W. Loewe and A. Kennemann, Archiv der Pharmazie, 1984, 317, 4372. S12

1 H and 13 C NMR spectra of all products 1 H and 13 C NMR spectra of 4a S13

1 H and 13 C NMR spectra of 4b O S O HN NH O S O HN NH S14

1 H and 13 C NMR spectra of 4c S15

1 H and 13 C NMR spectra of 4d S16

1 H and 13 C NMR spectra of 4e S17

1 H and 13 C NMR spectra of 4f S18

1 H and 13 C NMR spectra of 4g S19

1 H and 13 C NMR spectra of 4h S20

1 H and 13 C NMR spectra of 4i S21

1 H and 13 C NMR spectra of 4j S22

1 H and 13 C NMR spectra of 4k S23

1 H and 13 C NMR spectra of 4l S24

1 H and 13 C NMR spectra of 4m S25

1 H and 13 C NMR spectra of 4n S26

1 H and 13 C NMR spectra of 4o S27

1 H and 13 C NMR spectra of 4p O S O HN NH Br Br O S O HN NH Br Br S28

1 H and 13 C NMR spectra of 4q S29

1 H and 13 C NMR spectra of 4r O S O HN NH I I O S O HN NH I I S30

1 H and 13 C NMR spectra of 4s S31

1 H and 13 C NMR spectra of 4t S32

1 H and 13 C NMR spectra of 4u S33

1 H and 13 C NMR spectra of 6a S34

1 H and 13 C NMR spectra of 6b S35

1 H and 13 C NMR spectra of 8a S36

1 H and 13 C NMR spectra of 8b S37

1 H and 13 C NMR spectra of 8c S38